Method for producing isocyanate compound, method for producing carbamate compound, method for recovering amine compound

Abstract

The method for producing isocyanate compounds comprises: a step (1) for obtaining an N-substituted carbamate compound by reacting a primary amine compound and a carbonate derivative, while removing by-product compounds that have a boiling point lower than that of the N-substituted carbamate compound; a step (2) for obtaining an isocyanate compound using the reaction solution yielded by the step (1), by subjecting the N-substituted carbamate compound to thermal decomposition in the presence of an aprotic solvent and while removing the by-product hydroxy compound; a step (3) for separating the isocyanate compound and aprotic solvent from the reaction solution yielded by the step (2); and a step (4) for purifying the isocyanate compound by removing, from the fraction obtained in the step (3), component that has a boiling point higher than that of the isocyanate compound.

Description

Technical Field

[0001] The present invention relates to a method for producing an isocyanate compound, a method for producing a carbamate compound, a method for recovering an amine compound, and an isocyanate composition. This application claims priority based on Japanese Patent Application Nos. 2021-182191, 2021-182194, and 2021-182195 filed in Japan on November 8, 2021, and Japanese Patent Application No. 2021-199645 filed in Japan on December 8, 2021, and incorporates the contents thereof herein.

Background Art

[0002] Isocyanates are widely used as raw materials for the production of polyurethane foams, polyureas, paints, adhesives, etc. The main industrial production method of isocyanates is the reaction of an amine compound and phosgene (phosgene method), and almost the entire global production volume is produced by the phosgene method. However, the phosgene method has many problems.

[0003] First, a large amount of phosgene is used as a raw material. Phosgene is extremely toxic, and special care is required for its handling to prevent exposure to workers, and special equipment for detoxifying waste is also necessary. Second, in the phosgene method, a large amount of highly corrosive hydrogen chloride is by-produced, so a process for detoxifying the hydrogen chloride is required, and the produced isocyanate often contains hydrolyzable chlorine. Therefore, when using an isocyanate produced by the phosgene method, it may have an adverse effect on the weather resistance and heat resistance of polyurethane products.

[0004] Against such a background, a method for producing an isocyanate compound without using phosgene is desired. As one of the methods for producing an isocyanate compound without using phosgene, a method (urea method) by thermal decomposition of a carbamate compound obtained by reacting an amine with at least one of urea and an N-unsubstituted carbamic acid ester and an alcohol (carbamation reaction) has been proposed (see, for example, Patent Document 1, etc.). It has long been known that an isocyanate and a hydroxy compound can be obtained by thermal decomposition of a carbamate compound (see, for example, Non-Patent Document 1). The basic reaction is exemplified by the following formula (A).

[0005] [Chemical formula]

[0006] (In formula (A), R is an a-valent organic group, R' is a monovalent organic group, and a is an integer of 1 or more.)

[0007] On the other hand, in the thermal decomposition reaction of a carbamate compound, various irreversible side reactions are likely to occur simultaneously, such as an undesirable thermal denaturation reaction of the carbamate compound and a condensation reaction of the isocyanate generated by the thermal decomposition. Examples of the side reactions include, for example, a reaction for forming an isocyanurate group represented by the following formula (B), a reaction for generating carbodiimides represented by the following formula (C), a reaction for forming a uretonimine group represented by the following formula (D), and a reaction for forming an allophanate group represented by the following formula (E) (see, for example, Non-Patent Documents 1 to 4, etc.).

[0008] [Chemical formula]

[0009] (In formulas (B) to (E), R a ~R h are each independently a monovalent organic group.)

[0010] These side reactions not only lead to a decrease in the yield and selectivity of the target isocyanate, but in the production of isocyanates, polymer-like solids may precipitate, making long-term operation difficult, such as clogging the reactor.

[0011] As methods for producing isocyanates using carbamate compounds as raw materials, various methods have been proposed so far. For example, Patent Documents 2 and 3 disclose a method for continuously producing polyisocyanate by thermal decomposition of a carbamate compound in the presence of a high-boiling solvent without a catalyst.

[0012] Also, Patent Document 4 discloses that at a relatively low temperature, advantageously in the presence or absence of at least one of a catalyst and a stabilizer under reduced pressure, without using a solvent, a monocarbonate can be decomposed in good yield. The decomposition products (monoisocyanate and alcohol) are removed from the boiling reaction mixture by distillation and separately collected by fractional condensation. A method of partially removing the reaction mixture to remove by-products formed by thermal decomposition is disclosed in a general form.

[0013] In addition, in the carbamation reaction, in order to obtain a sufficient carbamate yield, it is necessary to react a large excess of hydroxy compound at a high temperature.

[0014] The use of a catalyst is mentioned as a method for increasing the reaction rate. For example, Patent Document 1 discloses basic catalysts such as methylates, ethylates, and butylates (each isomer) of lithium, sodium, potassium, calcium, and barium, rare earth elements, antimony, bismuth, simple substances of these elements, and oxides, sulfides, and salts of these elements, boron simple substance and boron compounds, metals of the copper group, zinc group, aluminum group, carbon group, and titanium group in the periodic table, and metal oxides and sulfides of these metals, carbides and nitrides of the carbon group, titanium group, vanadium group, and chromium group elements excluding carbon in the periodic table.

[0015] In addition, Patent Document 5 discloses a method for producing carbamate using zinc toluenesulfonate as a catalyst.

[0016] In addition, as catalysts used in the production of carbamate, Patent Document 6 discloses two metal compounds, Patent Document 7 discloses a metal compound containing a non-coordinating anion, and Patent Document 8 discloses a compound containing one or more cations of metals from Group IIB, VB, VIIB, and VIII of the periodic table.

[0017] In addition, Patent Documents 9 to 11 disclose methods for producing carbamate that may use various metal compounds as catalysts.

[0018] In the phosgene method described above, isocyanate is produced by the reaction of amine and phosgene. However, it is known that an undesirable polymerization reaction such as an increase in the amount of isocyanate occurs, and as a result, high-boiling compounds having a boiling point higher than that of isocyanate such as multimers are produced. However, it is also known that in the production of isocyanate by the urea method, high-boiling compounds having a boiling point higher than that of isocyanate are produced after the isocyanate is recovered. The composition containing this high-boiling compound may become a highly viscous liquid or solid near room temperature, and blockage or the like may occur in the continuous production of isocyanate compounds. In addition, the high-boiling compound is a by-product derived from the isocyanate compound and the organic amine compound that is a raw material of the isocyanate compound, and it is industrially advantageous if it can be recovered as an active ingredient.

[0019] For example, Patent Document 12 discloses a method for separating isocyanate from a diisocyanate-containing organic residue under specific temperature and pressure conditions and discharging the residue by forced transportation.

[0020] Patent Documents 13 to 17 disclose post-treatment methods for residues generated in the production of isocyanate.

[0021] Patent Document 18 discloses a method for post-treating residues generated in the production of isocyanates, in which all by-produced gas components are absorbed as carbonates using an alkali metal.

[0022] Patent Document 19 discloses a method for post-treating distillation residues generated in the synthesis of tolylene diisocyanate by reacting them with water, in which the distillation residues are reacted with water continuously or semi-continuously in a backmix reactor in the presence of a hydrolyzate.

[0023] Patent Document 20 discloses a decomposition recovery method for recovering an isocyanate-based compound as a raw material by bringing the isocyanate-based compound into contact with high-temperature and high-pressure water containing at least one compound selected from the group consisting of ammonia and aliphatic amines.

[0024] Patent Document 21 discloses a method for decomposing residues generated in the production of isocyanates in the presence of high-temperature and high-pressure water and hydroxides of alkali metals or alkaline earth metals.

Prior Art Documents

Patent Documents

[0025]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Patent Document 7

Patent Document 8

Patent Document 9

[0026] [Non-Patent Document 1] Third Volume, “186. A. W. Hofmann: Ueber die aromatischen Cyanate.”, Reports of the German Chemical Society, Vol. 3, pp. 653 - 658, 1870. [Non-Patent Document 2] Dyer E et al., “Thermal Degradation of Alkyl N-Phenylcarbomates.”, Journal of American Chemical Society, Vol. 81, pp. 2138-2143, 1959. [Non-Patent Document 3] Ulrich H et al., “[2+2] Cycloaddition Reactions of Unsymmetrically substituted Carbodiimides.”, Journal of Heterocyclic Chemistry, Vol. 24, pp. 1121-1123, 1987. [Non-Patent Document 4] Schwetlick K et al., “Kinetics and Catalysis of Consecutive Isocyanate Reactions. Formation of Carbamates, Allophanates and lsocyanurates.”, Journal of the Chemical Society, Perkin transactions II, Vol. 2, pp. 395-402, 1995. [Summary of the Invention] [Problems to be Solved by the Invention]

[0027] However, in the method described in Patent Document 2, since isocyanate is evaporated and recovered, harsh temperature and pressure conditions are required when producing high-boiling isocyanate. Also, under such harsh conditions, there is a problem that the amount of high-boiling by-products mixed in increases. Furthermore, in the conventional method for producing isocyanate compounds without using phosgene, the isocyanate compound is produced via a ureido compound and a phenylcarbamate compound from an amine compound, but the reaction equilibrium constant K of each reaction step is 10 -3 or more and 10 -1There is a problem in that it is biased toward the original system to the following extent and the yield of the finally obtained isocyanate compound is low.

[0028] In the method described in Patent Document 1, high-temperature conditions are required to obtain a carbamate in a high yield. Further, a large excess of a hydroxy compound is used to suppress the modification of the carbamate. Therefore, a large-scale apparatus is required and a large amount of energy is consumed, resulting in poor productivity and high manufacturing costs.

[0029] As a means for improving the productivity of carbamate, methods using a simple substance or compound of a metal as a catalyst are disclosed in many patent documents including Patent Document 1. When a carbamate is used as a raw material for an isocyanate, it is desirable to separate the metal or its compound from the isocyanate because the metal or its compound modifies the isocyanate. However, the metal or its compound is very difficult to volatilize and may impose restrictions on the process design.

[0030] In the method of Patent Document 12, when transporting a diisocyanate-containing organic residue to an apparatus for separating diisocyanate, the viscosity of the diisocyanate-containing organic residue tends to be relatively high, and the transportation itself is often difficult, and it is hard to say that it is a useful method.

[0031] In the methods described in Patent Documents 13 to 18, an isocyanate compound cannot be obtained sufficiently, and after the treatment step, it is necessary to further thermally decompose the carbamate to isocyanate, and this thermally decomposed step added in terms of reaction principle also has a problem of by-products being by-produced. Further, the method of adding a carbonic acid ester has an essential problem of promoting a side reaction to generate a carbamate in which an organic amine compound generated by the treatment of the isocyanate compound reacts with the carbonic acid ester. Furthermore, when the component containing a high-boiling compound after recovering the isocyanate is solid, it is industrially difficult to treat it in a continuous process. Therefore, it is necessary to rely on a batch process, and it is hard to say that it is a useful method in terms of poor economic efficiency.

[0032] The method described in Patent Document 19 has problems such as low reaction efficiency and a long time required for the completion of the reaction.

[0033] In the method described in Patent Document 20, the reaction efficiency depends on the interfacial contact efficiency between the aqueous phase and the organic phase, and there is a problem that liquid-liquid separation occurs in the part without stirring power and the reaction efficiency is low.

[0034] The method described in Patent Document 21 has a problem that the carbonate of an alkali metal or alkaline earth metal added to the reaction solution precipitates as a solid content and causes adhesion in the apparatus during a separation operation such as distillation.

[0035] As described above, various studies have been made on the method for producing isocyanate by thermal decomposition of a carbamate compound. However, there is a problem that it is difficult to continuously produce for a long time due to the generation of by-products having a boiling point higher than that of the target isocyanate compound and the adhesion of the by-products to the reactor. Therefore, in fact, it is hardly carried out industrially.

[0036] The present invention has been made in view of the above circumstances, and provides a novel method for producing an isocyanate compound, which has a good yield of the isocyanate compound, enables stable continuous operation, and suppresses the amount of by-products mixed therein.

[0037] Further, the present invention has been made in view of the above circumstances, and provides a method for producing a carbamate compound that does not use a metal catalyst, is inexpensive, and has a good yield, and a method for producing an isocyanate compound using the carbamate compound obtained by the production method.

[0038] Further, the present invention has been made in view of the above circumstances, and provides a method for recovering an amine compound that can efficiently regenerate a useful component containing the amine compound from the liquid phase component remaining after the production of the isocyanate compound.

[0039] Furthermore, the present invention has been made in view of the above circumstances, and provides an isocyanate composition capable of preventing the adhesion of by-products to the apparatus and improving the yield of the isocyanate compound when producing an isocyanate compound without using phosgene, and a method for producing an isocyanate compound using the isocyanate composition.

Means for Solving the Problems

[0040] That is, the present invention includes the following aspects. 〈1〉 A step (1) of reacting a primary amine compound with a carbonic acid derivative to obtain an N-substituted carbamate compound while extracting a compound having a lower boiling point than the by-produced N-substituted carbamate compound. Using the reaction solution containing the N-substituted carbamate compound obtained in the step (1), in the presence of an aprotic solvent, thermally decomposing the N-substituted carbamate compound to obtain an isocyanate compound while extracting the by-produced hydroxy compound. Step (2). A step (3) of separating the isocyanate compound and the aprotic solvent from the reaction solution containing the isocyanate compound obtained in the step (2). A step (4) of purifying the isocyanate compound by removing a component having a higher boiling point than the isocyanate compound from the fraction containing the isocyanate compound obtained in the step (3). A method for producing an isocyanate compound, comprising: 〈2〉 Further comprising a step (5) of hydrolyzing the fraction containing the aprotic solvent separated in the step (3) or a component having a higher boiling point than the isocyanate compound removed in the step (4) in the coexistence of an alkali and water to obtain the primary amine compound and the hydroxy compound. The method for producing an isocyanate compound according to <1>. 〈3〉 In the step (1), In the presence of a hydroxy compound, reacting a primary amine compound with urea or a urea derivative as the carbonic acid derivative to obtain an N-substituted carbamate compound while extracting a compound having a lower boiling point than the by-produced N-substituted carbamate compound, or React a primary amine compound with a carbonate ester as the carbonic acid derivative, and extract a hydroxy compound as a compound having a lower boiling point than the by-produced N-substituted carbamate compound while obtaining the N-substituted carbamate compound. The method for producing an isocyanate compound according to <1> or <2>. <4> In the step (2), while extracting the by-produced hydroxy compound into the gas phase, obtain a liquid phase containing the isocyanate compound. The method for producing an isocyanate compound according to any one of <1> to <3>. <5> The step (1) and the step (2) are carried out using one or more reactors selected from the group consisting of a tank reactor, a distillation column, a tubular evaporator, a thin-film evaporator, and a falling-film evaporator. The method for producing an isocyanate compound according to any one of <1> to <4>. <6> In at least one of the step (1) and the step (2), carry out by a reactive distillation method. The method for producing an isocyanate compound according to any one of <1> to <5>. <7> Recycle and reuse the hydroxy compound extracted in the step (2) in the step (1). The method for producing an isocyanate compound according to any one of <1> to <6>. <8> Recycle and reuse the aprotic solvent separated in the step (3) in the step (2). The method for producing an isocyanate compound according to any one of <1> to <7>. <9> The aprotic solvent is a carbonate ester. The method for producing an isocyanate compound according to any one of <1> to <8>. <10> In the step (4), in the presence of a carbonyl compound represented by the following general formula (I) in an amount of 1 mass ppm or more and 50 mass% or less based on the mass of the fraction containing the isocyanate compound, purify the isocyanate compound. The method for producing an isocyanate compound according to any one of <1> to <9>.

[0041]

Chemical formula

[0042] (In general formula (I), R 11 is an organic group having a valence of (n11 + n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is 2 or more and 8 or less.)

[0043] <11> The method for producing an isocyanate compound according to any one of <1> to <10>, wherein the primary amine compound is a compound represented by the following general formula (II).

[0044]

Chemical formula

[0045] (In general formula (II), R 21 is an organic group having a valence of n21. n21 is an integer of 2 or more.)

[0046] <12> The method for producing an isocyanate compound according to <11>, wherein n21 is 3 or more.

[0047] <13> A method for producing a carbamate compound, comprising a reaction step of reacting a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the presence of an amine compound having no active hydrogen to obtain a carbamate compound. <14> The method for producing a carbamate compound according to <13>, wherein the amine compound having no active hydrogen has one or more functional groups selected from the group consisting of a tertiary amino group, a nitrogen-containing aromatic group, an amidine group, and a guanidine group. <15> The method for producing a carbamate compound according to <14>, wherein the amine compound having no active hydrogen has one or more tertiary amino groups and has 3 or more and 85 or less carbon atoms. <16> The method for producing a carbamate compound according to <15>, wherein the amine compound having no active hydrogen has 1 or more and 6 or less tertiary amino groups and has 3 or more and 30 or less carbon atoms. <17> The method for producing the carbamate compound according to <16>, wherein the amine compound having no active hydrogen is N,N'-dimethylaniline, N,N'-diethylaniline, N-methyl-N'-ethylaniline, N,N'-dimethylaminopyridine, N,N,N',N'-tetramethylphenylenediamine, methylenebis(N,N'-dimethylaniline), triethylamine, ethyldiisopropylamine, N-methylmorpholine, N-methylpiperidine, quinuclidine, N,N'-dimethylpiperazine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N'-tetramethylxylylenediamine, pentamethyldiethylenetriamine, bis(2-morpholinoethyl)ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine, or hexamethylenetetramine. <18> The method for producing the carbamate compound according to <14>, wherein the amine compound having no active hydrogen has one or more nitrogen-containing aromatic groups and has 3 to 85 carbon atoms. <19> The method for producing the carbamate compound according to <18>, wherein the nitrogen-containing aromatic group is a substituted or unsubstituted pyridyl group, imidazolyl group, pyrazolyl group, quinolyl group, isoquinolyl group, oxazolyl group, thiazolyl group, pyridazinyl group, or pyrimidinyl group, pyrazyl group. <20> The method for producing the carbamate compound according to <19>, wherein the amine compound having no active hydrogen is pyridine, picoline, lutidine, collidine, 1-methylimidazole, 1-methylpyrazole, quinolone, isoquinolone, methylquinolone, oxazole, thiazole, pyridazine, pyrimidine, or pyrazine. <21> The method for producing the carbamate compound according to <14>, wherein the amine compound having no active hydrogen is an amidine group-containing compound represented by the following general formula (VIII-1).

[0048]

Chemical formula

[0049] (In general formula (VIII-1), R 811 , R 812 , R 813 , and R 814 are each independently a monovalent organic group. R 811 and R 812 , R 812 and R 813 , R 813 and R 814 , R 814 and R 811 may each independently combine with each other to form a ring structure. R 811 , R 812 , R 813 , and R 814 have a total carbon number of 5 or more and 85 or less.)

[0050] 〈22〉 The method for producing a carbamate compound according to 〈21〉, wherein the amidine group-containing compound has one or more ring structures, and the total carbon number of the R 811 , the R 812 , the R 813 , and the R 814 is 5 or more and 30 or less. 〈23〉 The method for producing a carbamate compound according to 〈22〉, wherein the amidine group-containing compound is 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo-[5.4.0]undec-7-ene, or 1,5-diazabicyclo-[4.3.0]nona-5-ene. 〈24〉 The method for producing a carbamate compound according to 〈14〉, wherein the amine compound having no active hydrogen is a guanidine group-containing compound represented by the following general formula (VIII-2).

[0051]

Chemical formula

[0052] (In general formula (VIII-2), R 821 , R 822 , R 823 , R 824 , and R 825is each independently a monovalent organic group. R 821 and R 822 、R 822 and R 823 、R 823 and R 824 、R 824 and R 825 、R 825 and R 821 may each independently combine with each other to form a ring structure. R 821 、R 822 、R 823 、R 824 、and R 825 The total carbon number of ) is 5 or more and 85 or less.

[0053] 〈25〉 The method for producing a carbamate compound according to 〈24〉, wherein the total carbon number of the R 821 、the R 822 、the R 823 、the R 824 、and the R 825 is 5 or more and 30 or less. 〈26〉 The method for producing a carbamate compound according to 〈25〉, wherein the guanidine group-containing compound is pentamethylguanidine or 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. 〈27〉 The method for producing a carbamate compound according to any one of 〈13〉 to 〈26〉, wherein the primary amine compound is an aliphatic or aromatic primary polyamine compound. 〈28〉 The method for producing a carbamate compound according to any one of 〈13〉 to 〈27〉, wherein the hydroxy compound is an aromatic hydroxy compound. 〈29〉 A method for producing an isocyanate compound, comprising a thermal decomposition step of thermally decomposing a carbamate compound obtained by the method for producing a carbamate compound according to any one of 〈13〉 to 〈28〉.

[0054] 〈30〉 A method for recovering an amine compound represented by the following general formula (IIa) from a liquid phase component containing a compound having a higher boiling point than the isocyanate compound by-produced in the method for producing an isocyanate compound represented by the following general formula (VIIa), A recovery method including a step (a) of reacting the liquid-phase component, an aromatic hydroxy compound, an active hydrogen-containing compound, and a catalyst in a reactor to obtain a reaction liquid containing an amine compound represented by the general formula (IIa).

[0055]

Chemical formula

[0056] (In the general formula (VIIa), R 71a is an organic group with a valence of n71a. n71a is an integer of 2 or more and 8 or less.)

[0057]

Chemical formula

[0058] (In the general formula (IIa), R 21a is an organic group with a valence of n21a, and satisfies the relational expression: R 21a =R 71a . n21a is an integer of 2 or more and 8 or less, and satisfies the relational expression: n21a = n71a.)

[0059] 〈31〉 The recovery method according to 〈30〉, wherein the step (a) includes the following step (a1) and step (a2). Step (a1) of mixing the liquid-phase component and the aromatic hydroxy compound; Step (a2) of reacting the mixture obtained in the step (a1) with an active hydrogen-containing compound and a catalyst in a reactor to obtain a reaction liquid containing an amine compound represented by the general formula (IIa) 〈32〉 The recovery method according to 〈31〉, wherein the step (a2) includes the following step (a2-1) and step (a2-2). Step (a2-1) of mixing the mixture obtained in the step (a1) with an amine compound as an active hydrogen-containing compound and a catalyst; A step (a2-2) of reacting the mixture obtained in the step (a2-1) with water as an active hydrogen-containing compound in a reactor to obtain a reaction solution containing an amine compound represented by the general formula (IIa). <33> The recovery method according to any one of <30> to <32>, wherein the active hydrogen-containing compound is water. <34> The recovery method according to any one of <30> to <32>, wherein the active hydrogen-containing compound is water and a primary amine compound. <35> The recovery method according to <34>, wherein the primary amine compound is an amine compound represented by the general formula (IIa). <36> In the method for producing an isocyanate compound represented by the general formula (VIIa), the recovery method according to any one of <30> to <35>, wherein a carbonic acid derivative, a hydroxy compound, and an amine compound represented by the general formula (IIa) are used as raw materials. <37> The liquid-phase component is a reaction solution containing a carbamate compound generated from a carbonic acid derivative, a hydroxy compound, and an amine compound represented by the general formula (IIa). The reaction solution is subjected to a thermal decomposition reaction, and the composition containing the isocyanate compound represented by the general formula (VIIa) thus generated is supplied to a distillation apparatus. When the isocyanate compound represented by the general formula (VIIa) is separated as a gas-phase component, the recovery method according to any one of <30> to <36>, which is the liquid-phase component withdrawn from the distillation apparatus. <38> The recovery method according to any one of <30> to <37>, wherein the liquid-phase component contains a compound having one or more functional groups selected from the group consisting of a group represented by the following formula (IX-1), a group represented by the following formula (IX-2), a group represented by the following formula (IX-3), a group represented by the following formula (IX-4), a group represented by the following formula (IX-5), a group represented by the following formula (IX-6), a group represented by the following formula (IX-7), a group represented by the following formula (IX-8), a group represented by the following formula (IX-9), a group represented by the following formula (IX-10), a group represented by the following formula (IX-11), and a group represented by the following formula (IX-12).

[0060] [Chemical formula]

[0061] (In Formulas (IX-1) to (IX-12), the wavy line indicates a bond.)

[0062] <39> The recovery method according to <38>, wherein the liquid-phase component contains a compound having two or more functional groups selected from the group consisting of the group represented by the formula (IX-1), the group represented by the formula (IX-2), the group represented by the formula (IX-3), the group represented by the formula (IX-4), the group represented by the formula (IX-5), the group represented by the formula (IX-6), the group represented by the formula (IX-7), the group represented by the formula (IX-8), the group represented by the formula (IX-9), the group represented by the formula (IX-10), the group represented by the formula (IX-11), and the group represented by the formula (IX-12). <40> The recovery method according to any one of <30> to <39>, wherein the catalyst is at least one compound selected from the group consisting of hydroxides and oxides of alkali metals, hydroxides and oxides of alkaline earth metals, tertiary amine compounds, metal oxides of Group 12, metal oxides of Group 13, and metal oxides of Group 14. <41> The recovery method according to <40>, wherein the catalyst is at least one compound selected from the group consisting of hydroxides and oxides of alkali metals and hydroxides and oxides of alkaline earth metals. <42> The recovery method according to <41>, wherein the catalyst is hydroxides and oxides of alkali metals. <43> The recovery method according to any one of <30> to <42>, further including the following steps (b) and (c). Step (b) of separating the amine compound represented by the general formula (IIa) from the reaction solution containing the amine compound represented by the general formula (IIa); Step (c) of purifying the amine compound represented by the general formula (IIa) <44> The recovery method according to <43>, further including the following step (d). In the method for producing an isocyanate compound represented by the general formula (VIIa), a step (d) of recycling the amine compound represented by the general formula (IIa) purified in the step (c) as a raw material <45> The recovery method according to any one of <30> to <44>, further including the following steps (e) and (f). Step (e) of separating a hydroxy compound from the reaction solution containing the amine compound represented by the general formula (IIa); Step (f) of purifying the hydroxy compound <46> The recovery method according to <45>, further including the following step (g). In the method for producing an isocyanate compound represented by the general formula (VIIa), a step (g) of recycling the hydroxy compound purified in the step (f) as a raw material <47> The recovery method according to <45>, further including the following step (h). Step (h) of recycling at least one residual liquid selected from the group consisting of the residual liquid after separating the amine compound represented by the general formula (IIa) in the step (b), the residual liquid after purifying the amine compound represented by the general formula (IIa) in the step (c), the residual liquid after separating the hydroxy compound in the step (e), and the residual liquid after purifying the hydroxy compound in the step (f) in the step (a)

[0063] <48> An isocyanate composition comprising a carbonyl compound represented by the following general formula (I), a modified product of the isocyanate compound, in which a part of the isocyanate groups of the isocyanate compound is converted into one or more functional groups selected from the group consisting of an isocyanurate group, a carbodiimide group, a uretonimine group, and an allophanate group, wherein the isocyanate compound and the carbonyl compound are different compounds, An isocyanate composition in which the value of {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of uretonimine group)+2×(molar amount of allophanate group)}÷(molar amount of carbonyl compound) is 0.001 or more and 8.0 or less.

[0064]

Chemical formula

[0065] (In general formula (I), R 11 is an organic group having a valence of (n11 + n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is an integer of 2 or more and 8 or less.)

[0066] 〈49〉 The R 11 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have 1 to 4 ester groups or a nitrogen atom, or a divalent to trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and the R 12 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom, in the isocyanate composition according to 〈48〉. 〈50〉 The isocyanate composition according to 〈48〉 or 〈49〉, wherein the isocyanate compound is a compound represented by the following general formula (VIIb).

[0067]

Chemical formula

[0068] (In general formula (VIIb), R 71b is an organic group having a valence of n71b, and the relational expression: R 71b = R 11 is satisfied. n71b is an integer of 2 or more and 8 or less, and the relational expression: n71b = n11 + n12 is satisfied.)

[0069] <51> The isocyanurate group, the carbodiimide group, the uretonimine group, and the allophanate group are groups represented by the following general formulas (X-1), (X-2), (X-3), and (X-4), respectively, and the isocyanate composition according to any one of <48> to <50>.

[0070]

Chemical formula

[0071] (In general formulas (X-1) to (X-4), R 101 , R 102 , R 103 , and R 104 are each independently an organic group having a valence of 2 or more and 8 or less, and the relational expressions: R 101 = R 71b , R 102 = R 71b , R 103 = R 71b , and R 104 = R 71b are satisfied. R 105 is a monovalent organic group, and the relational expression: R 105 = R 12 is satisfied. The wavy line indicates a bond.)

[0072] <52> With respect to the total mass of the isocyanate composition, the content of the isocyanate compound is 1% by mass or more and 99% by mass or less, and the total content of the carbonyl compound and the modified product of the isocyanate compound is 1% by mass or more and 99% by mass or less, and the isocyanate composition according to any one of <48> to <51>. <53> With respect to the total mass of the isocyanate composition, the isocyanate composition according to any one of <48> to <52> further contains one or more compounds selected from the group consisting of a carbamate group-containing compound represented by the following general formula (XI) and a carbonate ester represented by the following general formula (III-1a), each being 2.0 ppm by mass or more and 99% by mass or less.

[0073] [Chemistry]

[0074] (In general formula (XI), R 111 is an organic group with a valence of (n111 + n112), and the relational expression: R 111 = R 11 is satisfied. R 112 is a monovalent organic group, and the relational expression: R 112 = R 12 is satisfied. n111 is an integer from 1 to 8, n112 is an integer from 0 to 7, the sum of n111 and n112 is an integer from 2 to 8, and the relational expression: n111 + n112 = n11 + n12 is satisfied.)

[0075] [Chemistry]

[0076] (In general formula (III-1a), R 311a and R 312a are each independently a monovalent organic group, and the relational expression: R 311a = R 312a = R 12 is satisfied.)

[0077] 〈54〉 The isocyanate composition according to 〈53〉, containing one or more compounds selected from the group consisting of the carbamate group-containing compound represented by the general formula (XI) and the carbonate ester represented by the general formula (III-1a), each in an amount of 2.0 mass ppm or more and 1.0 × 10 4 mass ppm or less based on the total mass of the isocyanate composition. 〈55〉 A method for producing an isocyanate compound, comprising distilling and purifying the isocyanate composition according to any one of 〈48〉 to 〈54〉 and continuously recovering the isocyanate compound as a gas-phase component. [Advantages of the Invention]

[0078] According to the manufacturing method of the above aspect, the yield is good, stable continuous operation is possible, and the amount of by-products mixed in can be suppressed.

[0079] Moreover, according to the manufacturing method of the carbamate compound of the above aspect, it is possible to provide a manufacturing method of a carbamate compound that does not use a metal catalyst, is inexpensive, and has a good yield.

[0080] Moreover, according to the recovery method of the above aspect, useful components containing an amine compound can be efficiently regenerated from the liquid phase component remaining after the production of the isocyanate compound.

[0081] Moreover, according to the isocyanate composition of the above aspect, when producing an isocyanate compound without using phosgene, it is possible to provide an isocyanate composition that can prevent by-products from adhering to the apparatus and improve the yield of the isocyanate compound. The manufacturing method of the isocyanate compound of the above aspect is a method using the isocyanate composition, and can prevent by-products from adhering to the apparatus and improve the yield of the isocyanate compound.

Brief Description of the Drawings

[0082]

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Embodiments for Carrying Out the Invention

[0083] Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as "this embodiment") will be described in detail. Note that the present invention is not limited to the following embodiments, and various modifications can be made and implemented within the scope of the gist thereof.

[0084] In this specification, when referring to the IUPAC rules and the Nomenclature rules defined by IUPAC shown hereinafter (except when specifically citing IUPAC recommendations of other years, etc.), based on Recommendations 1979, all the rules of organic chemistry and biochemistry published as a separate volume of "Chemical Areas" in 1980 and the Japanese translation rules are used as the basis, and all subsequent revisions and recommendations are added. It means citing "Organic Chemistry and Biochemistry Nomenclature" (revised second edition published by Nankodo, Japan in 1992). "Organic" refers to the general group of compounds targeted by the nomenclature disclosed in the nomenclature. The target may be the one described in the recommendations issued in 1993. However, the "organic" compounds targeted by the above Nomenclature also include organometallic compounds and metal complexes. In this embodiment, unless otherwise specified, terms such as "organic group" and "substituent" mean groups composed of atoms that do not include metal atoms and metalloids. Further, in this embodiment, preferably, "organic compounds", "organic groups" or "substituents" composed of atoms selected from H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom), and I (iodine atom) are used.

[0085] The terms "aliphatic" and "aromatic" are frequently used in the following description. According to the above-mentioned IUPAC rules, it is described that organic compounds are classified into aliphatic compounds and aromatic compounds. An aliphatic compound is a definition of a group in accordance with aliphatic compounds based on the 1995 IUPAC recommendations. In this recommendation, an aliphatic compound is defined as "Acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds".

[0086] In addition, the "aliphatic compound" used in the description of this embodiment contains both saturated and unsaturated, linear and cyclic ones, and refers to an "organic compound", "organic group" or "substituent" composed of atoms selected from the group consisting of the above-mentioned halogen atoms of H (hydrogen atom); C (carbon atom); N (nitrogen atom); O (oxygen atom); S (sulfur atom); Si (silicon atom); Cl (chlorine atom), Br (bromine atom) or I (iodine atom).

[0087] When an aromatic group such as an aralkyl group is bonded to an aliphatic group, it may be expressed as an "aliphatic group substituted with an aromatic group" or a "group consisting of an aliphatic group bonded with an aromatic group" in this way. This is based on the reactivity in this embodiment, because the properties related to the reaction of a group such as an aralkyl group are extremely similar to the aliphatic reactivity rather than aromaticity.

[0088] In addition, non-aromatic reactive groups including aralkyl groups, alkyl groups, etc. may be expressed as "aliphatic groups optionally substituted with aromatic groups", "aliphatic groups optionally bonded with aromatic groups", etc.

[0089] When explaining the general formula of a compound used in this specification, the definition in accordance with the Nomenclature rules defined by IUPAC mentioned above is used, but common names may be used for the names of specific groups and the names of exemplified compounds. In addition, when the number of atoms, the number of substituents, and the number are described in this specification, they all represent integers.

[0090] "Active hydrogen" as used in this specification refers to hydrogen atoms bonded to oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc., and hydrogen atoms of terminal methine groups. Although the hydrogen of a hydroxy group is also active hydrogen, the hydroxy group is also included in the composition containing the product obtained by the production method of this embodiment and the reaction solution containing the reaction raw materials, and it is not a group that has an adverse effect. Therefore, unless otherwise specified, hydroxy groups are excluded from the groups containing active hydrogen. "Active hydrogen" is, for example, hydrogen contained in atomic groups such as -OH group, -C(=O)OH group, -C(=O)H group, -SH group, -SO3H group, -SO2H group, -SOH group, -NH2 group, -NH- group, -SiH group, -C≡CH group, etc.

[0091] In addition, examples of the compound having a hydroxy group (-OH group) include alcohols and aromatic hydroxy compounds.

[0092] "Alcohol" as used in this specification is a compound described in the IUPAC definition (Rule C-201), "Compounds in which a hydroxy group, -OH, is attached to a saturated carbon atom: R3COH", and does not include aromatic hydroxy compounds in which a hydroxy group is bonded to an aromatic ring.

[0093] "Aromatic hydroxy compound" as used in this specification is a phenol described in the IUPAC definition (Rule C-202), "Compounds having one or more hydroxy groups attached to a benzene or other arene ring."

[0094] ≪Method for Producing Isocyanate Compound≫ The method for producing an isocyanate compound according to this embodiment (hereinafter, may be simply referred to as "the production method of this embodiment") includes the following steps (1) to (4). Step (1) of reacting a primary amine compound with a carbonic acid derivative to obtain an N-substituted carbamate compound while extracting a compound having a lower boiling point than the by-produced N-substituted carbamate compound (hereinafter, also referred to as "low-boiling compound"); Step (2) of thermally decomposing the N-substituted carbamate compound in the presence of an aprotic solvent using the reaction solution containing the N-substituted carbamate compound obtained in the above step (1) to obtain an isocyanate compound while extracting the by-produced hydroxy compound; Step (3) of separating the isocyanate compound and the aprotic solvent from the reaction solution containing the isocyanate compound obtained in the above step (2); Step (4) of purifying the isocyanate compound by removing a component having a higher boiling point than the isocyanate compound (hereinafter, may be simply referred to as "high-boiling component") from the fraction containing the isocyanate compound obtained in the above step (3).

[0095] In the production method of this embodiment, while extracting the low-boiling compound by-produced in the above step (1), the production reaction of the N-substituted carbamate compound is carried out, and while extracting the hydroxy compound by-produced in the above step (2), the production reaction of the isocyanate compound is carried out. Thus, in the reactions of steps (1) and (2) where the reaction equilibrium constant K is about 10 -3 or more and 10 -1 or less and biased towards the original system, the reaction equilibrium can be shifted to the product side, and the yield of the isocyanate compound can be improved. Further, in the above step (4), since the high-boiling component in the fraction containing the isocyanate compound functions as a solvent, the amount of the high-boiling component mixed in is suppressed, and the isocyanate compound can be isolated and purified with high purity.

[0096] Hereinafter, each step of the production method of this embodiment will be described in detail. Also, details of the raw materials used and the products obtained in each step will be described later.

[0097] <Step (1): Process for producing N-substituted carbamate compound> In Step (1), a primary amine compound and a carbonic acid derivative are reacted to obtain an N-substituted carbamate compound while extracting a by-produced low-boiling compound.

[0098] Step (1) can also be referred to as the process for producing an N-substituted carbamate compound. In Step (1), the terminal amino group of the primary amine compound is converted by the reaction of the primary amine compound and the carbonic acid derivative, and an N-substituted carbamate compound is obtained.

[0099] Here, when urea is used as the carbonic acid derivative, in the presence of a hydroxy compound, after a reaction intermediate in which the terminal amino group of the primary amine compound becomes a ureido group is generated, the terminal ureido group further reacts with the hydroxy compound, and the terminal ureido group is substituted with a residue obtained by removing a hydroxyl group from the hydroxy compound via a carbamate group, that is, an N-substituted carbamate compound is obtained. At this time, the by-produced low-boiling compound becomes ammonia.

[0100] Also, when a urea derivative (a compound represented by the general formula (IV) described later) is used as the carbonic acid derivative, the by-produced low-boiling compound is one or more compounds selected from the group consisting of ammonia and an alkylamine corresponding to an alkyl group substituting the amino group of urea.

[0101] In Step (1), the case where urea is used as the carbonic acid derivative is described below. There is no particular limitation as long as it is a method capable of simultaneously performing the production reaction of the N-substituted carbamate compound via the above ureide intermediate and extracting the by-produced ammonia. However, step (1) is preferably carried out using a distillation column, a tubular evaporator, a thin-film evaporator, or a falling-film evaporator, more preferably a distillation column, a thin-film evaporator, or a falling-film evaporator, even more preferably a distillation column or a falling-film evaporator, and particularly preferably using a distillation column. When using a distillation column, since it involves chemical changes and reactions in this step, it is preferably carried out by a technique called reactive distillation. The reactive distillation method is a method in which the above-described reaction of a mixture of a hydroxy compound, a primary amine compound, and one or more compounds selected from the group consisting of urea and urea derivatives is carried out in a reactor, and the by-produced ammonia is extracted from the above reactor by distillation. Since ammonia has a lower boiling point than the main product, the N-substituted carbamate compound, by extracting ammonia, which is a by-product, as a gas-phase component, a fraction containing the N-substituted carbamate compound can be efficiently obtained as a liquid-phase component.

[0102] Also, step (1) is preferably carried out by a continuous method. The continuous method is a method in which the above-described mixture is continuously supplied to a reactor to carry out the production reaction of the N-substituted carbamate compound via the ureide intermediate, and the by-produced ammonia is continuously extracted from the above reactor. The supply rate of the above-described mixture to the reactor and the extraction rate of ammonia can be appropriately adjusted according to the production rates of the product, the N-substituted carbamate compound, and ammonia.

[0103] The usage amounts of the primary amine compound and one or more compounds selected from the group consisting of urea and urea derivatives can be such that the molar ratio of the amino group of the primary amine compound to the urea group of the above compound is 1:3 to 3:1, preferably 1:2 to 2:1, more preferably 1:1.5 to 1.5:1, and even more preferably 1:1. By the usage amounts of the above two compounds being within the above range, the ureidation reaction can be carried out more efficiently.

[0104] The amount of the hydroxy compound used is preferably an amount such that the molar ratio of the hydroxyl group of the hydroxy compound to the amino group of the primary amine compound is 1 / 1 or more and 300 / 1 or less, more preferably 1 / 1 or more and 250 / 1 or less, and even more preferably 1 / 1 or more and 200 / 1 or less. When the molar ratio of the hydroxyl group of the hydroxy compound to the amino group of the primary amine compound is an amount equal to or higher than the above lower limit value, the carbamate group can be generated more efficiently. On the other hand, when the amount is equal to or lower than the above upper limit value, the amount of the hydroxy compound used can be further reduced while maintaining the production efficiency of the carbamate group.

[0105] In addition, in order to quickly recover the low-boiling decomposition products, a reactor carrier can be introduced, and the gaseous component containing the carrier can be discharged from the pyrolysis reactor. The "carrier" referred to here means a substance that is substantially inert and in a gaseous state under the pyrolysis reaction conditions.

[0106] Specific examples of such carriers include, for example, inert gases, hydrocarbon gases, etc. Examples of inert gases include nitrogen, argon, helium, carbon dioxide gas, methane, ethane, propane, etc. Among them, as the carrier, an inert gas such as nitrogen is preferable.

[0107] Low-boiling organic solvents may also be used to achieve a similar effect. Examples of low-boiling organic solvents include halogenated hydrocarbons, lower hydrocarbons, ethers, etc. Examples of halogenated hydrocarbons include dichloromethane, chloroform, carbon tetrachloride, etc. Examples of lower hydrocarbons include pentane, hexane, heptane, benzene, etc. Examples of ethers include tetrahydrofuran, dioxane, etc.

[0108] These carriers may be used alone or in combination of two or more. In addition, these carriers are preferably preheated before use.

[0109] The reaction temperature varies depending on the type of primary amine compound used and the reaction pressure, but it is preferably 40°C or higher and 380°C or lower, more preferably 50°C or higher and 320°C or lower, even more preferably 60°C or higher and 300°C or lower, particularly preferably 80°C or higher and 300°C or lower, and most preferably 100°C or higher and 280°C or lower.

[0110] The reaction pressure varies depending on the type of compound used and the reaction temperature, but it may be any of reduced pressure, normal pressure, and increased pressure. The pressure is preferably in the range of 20 Pa or higher and 2×10 6 Pa or lower, more preferably in the range of 30 Pa or higher and 1.5×10 6 Pa or lower, even more preferably in the range of 50 Pa or higher and 1×0 6 Pa or lower, particularly preferably in the range of 50 Pa or higher and 0.5×0 6 Pa or lower.

[0111] The reaction time (the residence time in the case of the continuous method) is not particularly limited and is preferably 0.001 hour or longer and 100 hours or shorter, more preferably 0.005 hour or longer and 50 hours or shorter, and even more preferably 0.01 hour or longer and 10 hours or shorter.

[0112] Also, when a carbonic acid ester is used as the carbonic acid derivative, the terminal amino group of the primary amine compound and the carbonic acid ester react directly to be activated. A carbonic acid ester is a compound in which one or two hydrogen atoms of the two hydrogen atoms of carbonic acid CO(OH)2 are substituted with an alkyl group or an aryl group, and is a compound represented by the general formula (III) described later. At this time, a compound substituted with an alkyl group or an aryl group derived from the carbonic acid ester via a carbamate group, that is, an N-substituted carbamate compound is obtained. The by-produced low-boiling compound is a hydroxy compound composed of an alkyl group or an aryl group derived from the carbonic acid ester and a hydroxy group.

[0113] The reaction conditions for the carbonate ester and the primary amine compound vary depending on the compounds to be reacted, but the molar amount of the carbonate ester is preferably 1 time or more in stoichiometric ratio with respect to the molar amount of the terminal amino group of the primary amine compound, and more preferably 1.01 times or more and 1000 times or less. In order to increase the reaction rate and complete the reaction earlier, the molar amount of the carbonate ester is preferably in excess with respect to the molar amount of the terminal amino group of the primary amine. Considering the size of the carbamation reactor, an amount of 1.01 times or more and 50 times or less is more preferable, and an amount of 1.2 times or more and 10 times or less is particularly preferable.

[0114] The reaction between the carbonate ester and the primary amine compound is preferably carried out in the liquid phase using a solvent as appropriate. The solvent can be appropriately selected depending on the compounds to be used. For example, aliphatic hydrocarbons, aromatic hydrocarbons, aromatic hydroxy compounds, alcohols, oxygen atom-containing compounds such as ethers, sulfur atom compounds such as thiols and sulfides, halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons, and water can be used, and these compounds can also be used in appropriate combinations.

[0115] The primary amine compound is preferably present in a liquid state in the carbamation reactor. In that case, it is preferably supplied in a state dissolved in a solvent, and as the solvent for dissolving the primary amine compound, the solvents described above are preferably used. It is also preferable that the supply of the primary amine compound is carried out as a mixture with a hydroxy compound, water, or a carbonate ester.

[0116] The carbamation reaction in step (1) is carried out by supplying the carbonate ester and the primary amine compound to the carbamation reactor. The reaction temperature is preferably 0°C or higher and 150°C or lower. Although a high temperature is preferable to increase the reaction rate, from the viewpoint of suppressing undesirable side reactions, 10°C or higher and 100°C or lower is more preferable. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the carbamation reactor.

[0117] The reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, normal pressure, or increased pressure, usually in the range of 20 Pa or more and 1×10 6 Pa or less.

[0118] There is no particular limitation on the reaction time (residence time in the case of the continuous method), and usually 0.001 hours or more and 50 hours or less is preferable, 0.01 hours or more and 20 hours or less is more preferable, and 0.1 hours or more and 10 hours or less is even more preferable. Also, the reaction solution can be sampled, and for example, it can be confirmed by liquid chromatography that the desired amount of carbamic acid ester has been produced, and then the reaction can be terminated.

[0119] In this embodiment, in the reaction of the carbonic acid ester and the primary amine compound, a catalyst may or may not be used in addition to these compounds. When no catalyst is used, thermal denaturation of the carbamic acid ester due to the influence of the metal component derived from the catalyst can be prevented. When a catalyst is used, the reaction can be completed in a short time and the reaction temperature can be lowered. When a catalyst is used, for example, organometallic compounds or inorganic metal compounds such as tin, lead, copper, and titanium; alcoholates of alkali metals or alkaline earth metals, such as methylates, ethylates, or butylates (each isomer) of lithium, sodium, potassium, calcium, or barium, and other basic catalysts can be used.

[0120] In the reaction for producing the N-substituted carbamate compound, a reactor that meets the appropriate conditions is selected as appropriate. The reactor may be a plug flow reactor or a tank type reactor. Specifically, conventionally known reactors such as a stirred tank, a pressurized stirred tank, a vacuum stirred tank, a tower type reactor, a distillation column, a packed column, and a thin film evaporator can be used in appropriate combinations. In order to efficiently recover the gas phase components, preferably, a known distillation apparatus is used. For example, a distillation column, a multi-stage distillation column, a multi-tubular reactor, a tank type reactor, a continuous multi-stage distillation column, a tray column, a packed column, a thin film evaporator, a reactor equipped with a support inside, a forced circulation reactor, a falling film evaporator, a falling droplet evaporator, a falling film type evaporator including any one of these, and a method combining these, etc., various known methods are used. From the viewpoint of quickly removing the by-produced low-boiling compound from the reaction system, a structure with a large gas-liquid contact area that can quickly transfer the by-produced low-boiling compound to the gas phase is preferable. Among these, step (1) is particularly preferably carried out using one or more reactors selected from the group consisting of a tank type reactor, a distillation column, a tubular evaporator, a thin film evaporator, and a falling film type evaporator.

[0121] When using a packed column, as the solid packing material provided in the packed column, the packing materials generally used in distillation columns and absorption columns can be appropriately used. Specifically, preferable solid packing materials include, for example, Raschig rings, cascade mini rings, Lessing rings, spiral rings, ball rings, interlocking saddles, Steedman packing, McMahon packing, Dixon packing, helix packing, coil packing, heat pipe packing, etc. When the distillation column is a tray column, various tray columns having sieve trays, cascade trays, turbo grid trays, ripple trays, dual trays, etc. can be appropriately used.

[0122] The material of the solid filler is preferably inert to decomposition products and is not particularly limited, such as magnetic or metallic. Among them, as the material of the solid filler, a material with high thermal conductivity is preferred. In addition to SUS304, SUS316, and SUS316L, generally, silicon oxide (composition formula: SiO2), aluminum oxide (composition formula: Al2O3), and fluorocarbon (a compound having a repeating unit of -CHF- or CF2-) are preferred. Also, glass, ceramic, or fluororesin containing these as constituent components is also preferred. In the case of glass or ceramic, the contents of silicon oxide and aluminum oxide are not particularly limited, and the content of silicon oxide may occupy 60% by mass or more, or the content of aluminum oxide may occupy 60% by mass or more, and various materials can be selected.

[0123] The ceramic or ceramics referred to here means a sintered body obtained by firing inorganic substances. Here, regardless of whether it is a metal or a non-metal, it is a general term for inorganic solid materials such as semiconductors such as silicon, molded bodies, powders, and films of inorganic compounds such as carbides, nitrides, borides, and titanium oxides. Examples of fluororesins include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride - hexafluoropropylene copolymer, ethylene - tetrafluoroethylene copolymer, ethylene - chlorotrifluoroethylene copolymer, and the like. Other metal atoms may be contained within the scope not contrary to the gist of the present embodiment in the preferred fillers shown here.

[0124] The type of condenser provided in the reactor is not particularly limited, and known condensers can be used. For example, conventionally known condensers such as multitubular cylindrical condensers, double-tube condensers, single-tube condensers, and air-cooled condensers can be appropriately combined and used. The condenser may be provided inside the reactor, outside the reactor, or connected to the reactor by piping, and various forms are adopted in consideration of the type of reactor and condenser, the method of handling the condensate, etc. There are also no particular restrictions on the materials of the reactor and condenser, and known materials can be used as long as they do not have an adverse effect on the above N-substituted carbamate compound or isocyanate, which is the product. For example, those made of glass, stainless steel, carbon steel, Hastelloy, those with a glass lining on the base material, or those with a Teflon (registered trademark) coating can also be used. Among them, SUS304, SUS316, SUS316L, etc. can be preferably used because they are inexpensive. If necessary, instrumentation devices such as flow meters and thermometers, and known process devices such as reboilers, pumps, and condensers may be added. Heating may be by known methods such as steam and heaters, and cooling may also use known methods such as natural cooling, cooling water, and brine. Steps may be added as necessary.

[0125] In step (1), the reaction (ureidation reaction) to produce a reaction intermediate in which the terminal amino group of the primary amine compound becomes a ureido group by reacting the primary amine compound with one or more compounds selected from the group consisting of urea and urea derivatives, and the reaction to produce an N-substituted carbamate compound by reacting the reaction intermediate having a ureido group with a hydroxy compound may be carried out in the same reactor or in separate reactors. Regarding the ureidation reaction, conventionally known reactors such as stirred tanks, pressurized stirred tanks, vacuum stirred tanks, tower reactors, continuous stirred tank reactors, distillation towers, packed towers, plug flow reactors, and thin-film evaporators can be appropriately combined and used. Stirred tanks, pressurized stirred tanks, vacuum stirred tanks, tower reactors, continuous stirred tank reactors, or plug flow reactors are preferred, and from the perspective of production efficiency, it is more preferable to carry out the reaction continuously using a continuous stirred tank reactor or a plug flow reactor.

[0126] In addition, in step (1), other steps can be added as necessary. Examples of other steps include a step of producing a different N-substituted carbamate by performing a transesterification reaction of the N-substituted carbamate obtained in the above reaction with a hydroxy compound different from the hydroxy compound used in the above reaction; a step of separating part or all of the hydroxy compound from the reaction solution obtained in the above reaction; a step of recovering ammonia generated in the above reaction; a step of decomposing by-products and converting them into valuable substances, and the like. Further, in step (1), it is also one of the preferred embodiments to control the reaction conditions by appropriately refluxing as necessary.

[0127] <Step (2): Isocyanate compound production step (pyrolysis step)> In step (2), using the reaction solution containing the N-substituted carbamate compound obtained in step (1), the N-substituted carbamate compound is pyrolyzed in the presence of an aprotic solvent, and while extracting the by-produced hydroxy compound, an isocyanate compound is obtained.

[0128] Step (2) can also be referred to as an isocyanate compound production step or a pyrolysis step. In step (2), an isocyanate compound is obtained by the pyrolysis reaction of the N-substituted carbamate compound. Further, the by-produced hydroxy compound is the same as the hydroxy compound used in step (1) or the hydroxy compound derived from the carbonic ester used in step (1) (the hydroxy compound having a structure in which a hydroxy group is bonded to R or R in the compound represented by the following general formula (III-1)). 311 or R 312 and having a structure in which a hydroxy group is bonded).

[0129] In step (2), there is no particular limitation as long as it is a method capable of simultaneously performing the thermal decomposition reaction of the N-substituted carbamate compound and extracting the by-produced hydroxy compound. However, step (2) is preferably carried out using a stirring tank, a pressurized stirring tank, a depressurized stirring tank, a tower reactor, a continuous stirring reactor, a distillation column, a tubular evaporator, a thin-film evaporator, or a falling film evaporator. A distillation column, a thin-film evaporator, or a falling film evaporator is more preferable, a distillation column or a falling film evaporator is further preferable, and it is particularly preferable to use a distillation column. When using a distillation column, since a chemical change or the like occurs in this step, it is preferably carried out by a technique called reactive distillation. As step (2) using the reactive distillation method, it is a method of extracting the by-produced hydroxy compound from the reactor by distillation while performing the thermal decomposition reaction of the N-substituted carbamate compound in the reactor. In step (1) described above, it is preferable to use a hydroxy compound having a normal boiling point lower than that of the isocyanate compound as the main product. Thereby, the hydroxy compound as a by-product can be extracted as a gas-phase component, and a fraction containing the isocyanate compound can be obtained more efficiently as a liquid-phase component. The "normal boiling point" referred to here means the boiling point under 1 atm.

[0130] Also, it is preferable to use a hydroxy compound having a normal boiling point higher than that of the isocyanate compound as the main product. Thereby, the hydroxy compound can be extracted as a liquid-phase component, and a fraction containing the isocyanate compound can be obtained as a gas-phase component.

[0131] The difference in the normal boiling points between the isocyanate compound and the hydroxy compound is preferably 300 °C or less, more preferably 250 °C or less, and even more preferably 200 °C or less. On the other hand, the lower limit of the difference in the normal boiling points between the isocyanate compound and the hydroxy compound is usually 10 °C or more, preferably 25 °C or more, more preferably 50 °C or more, and even more preferably 100 °C or more. Since the difference in the standard boiling points between the isocyanate compound and the hydroxy compound is within the above range, the hydroxy compound after thermal decomposition can be efficiently extracted by the gas phase, the reverse reaction between the generated isocyanate compound and the hydroxy compound can be further reduced, and the yield of the isocyanate compound can be further improved.

[0132] Moreover, step (2) is preferably carried out by a continuous method. The continuous method is a method in which a reaction solution containing an N-substituted carbamate compound is continuously supplied to a reactor to carry out a thermal decomposition reaction of the N-substituted carbamate compound, and the by-produced hydroxy compound is continuously extracted from the reactor. The supply rate of the above reaction solution to the reactor and the extraction rate of the hydroxy compound can be appropriately adjusted according to the production rates of the product isocyanate compound and hydroxy compound.

[0133] From the viewpoint of further improving the yield of the isocyanate compound, the standard boiling point of the aprotic solvent is preferably lower than the standard boiling point of the isocyanate compound and higher than the hydroxy compound.

[0134] The difference in the standard boiling points between the isocyanate compound and the aprotic solvent is preferably 100 °C or less, more preferably 90 °C or less, and even more preferably 80 °C or less. On the other hand, the lower limit of the difference in the standard boiling points between the isocyanate compound and the aprotic solvent is usually 10 °C or more, preferably 15 °C or more, more preferably 20 °C or more, even more preferably 25 °C or more, and particularly preferably 30 °C or more. When the difference between the standard boiling point of the isocyanate compound and that of the aprotic solvent is equal to or less than the above upper limit value, when extracting the hydroxy compound after thermal decomposition into the gas phase, entrainment of the aprotic solvent can be more suppressed, and by preventing an increase in the concentration of isocyanate in the liquid phase, the reverse reaction between the generated isocyanate and the hydroxy compound, the modification reaction with the carbamate as the raw material, and the polymerization of isocyanates can be further reduced. On the other hand, when it is equal to or greater than the above lower limit value, in step (3) described later, the aprotic solvent and the isocyanate compound can be separated more efficiently, and the yield of the isocyanate compound can be further improved.

[0135] Also, the standard boiling point of the isocyanate compound is usually 150°C or higher, preferably 250°C or higher, more preferably 255°C or higher, still more preferably 300°C or higher, and particularly preferably 350°C or higher. On the other hand, the upper limit of the standard boiling point of the isocyanate compound is not particularly limited, but it is preferably 450°C or lower, more preferably 430°C or lower, and still more preferably 420°C or lower. When the standard boiling point of the isocyanate compound is equal to or higher than the above lower limit value, it tends to be more easily separated from the hydroxy compound which is a by-product in step (2). On the other hand, when the standard boiling point of the isocyanate compound is equal to or lower than the above upper limit value, it tends to be more easily separated from the aprotic solvent and high-boiling components in steps (3) and (4) described later.

[0136] The amount of the aprotic solvent used is not particularly limited, and it is usually used in the range of 0.1% by mass or more and 100,000% by mass or less, preferably 1% by mass or more and 10,000% by mass or less, more preferably 5% by mass or more and 5,000% by mass or less, still more preferably 10% by mass or more and 4,000% by mass or less, even more preferably 20% by mass or more and 3,000% by mass or less, particularly preferably 20% by mass or more and 2,500% by mass or less, and most preferably 30% by mass or more and 2,000% by mass or less, based on the total mass of the reaction solution containing the N-substituted carbamate compound as the raw material. When the amount of the aprotic solvent used is at least the above lower limit value, the concentration of the isocyanate compound produced is further decreased, and the formation of allophanate by the reaction of the isocyanate compounds with each other during thermal decomposition and the formation of allophanate by the reaction of the isocyanate compound with the raw material N-substituted carbamate compound can be further suppressed. The thermal decomposition yield of the isocyanate compound can be further improved, and the precipitation of the polymer can be further suppressed. On the other hand, when the amount of the aprotic solvent used is at most the above upper limit value, it becomes possible to further improve the production efficiency of the isocyanate compound in the same apparatus. Further, the reaction may be carried out using a single aprotic solvent, or a plurality of types of aprotic solvents may be used in combination, and they can be arbitrarily selected according to the reaction conditions.

[0137] The thermal decomposition temperature of the N-substituted carbamate compound varies depending on the type of the N-substituted carbamate compound used, but is preferably 140°C or higher and 380°C or lower, more preferably 160°C or higher and 320°C or lower, still more preferably 180°C or higher and 300°C or lower, particularly preferably 200°C or higher and 300°C or lower, and most preferably 220°C or higher and 280°C or lower. In order to keep the reaction temperature constant, a known cooling device and heating device may be installed in the above thermal decomposition reactor. When the thermal decomposition temperature is at least the above lower limit value, the thermal decomposition reaction of the N-substituted carbamate compound further proceeds, and the higher the temperature, the higher the thermal decomposition rate, and the thermal decomposition of the N-substituted carbamate compound is completed in a short time. On the other hand, when it is at most the above upper limit value, the denaturation reaction from isocyanate to allophanate or the like can be further suppressed. Further, since the amount of the polymer of isocyanate generated by allophanation can be further reduced, the adhesion to the reaction apparatus and the blockage of the piping can be further suppressed, and the operability can be further improved.

[0138] Further, the reaction pressure varies depending on the type of the compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure. The pressure can be set to the saturated vapor pressure of the aprotic solvent used, and is preferably carried out in the range of 20 Pa or higher and 10×10 6 Pa or lower. The reaction time (retention time in the case of the continuous method) is not particularly limited, and is preferably 0.001 hour or more and 100 hours or less, more preferably 0.005 hour or more and 50 hours or less, and even more preferably 0.01 hour or more and 10 hours.

[0139] In the thermal decomposition reaction, a catalyst is not necessarily required, but a catalyst may be used to lower the reaction temperature or complete the reaction earlier. The catalyst is preferably used in an amount of 0.01% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, based on the mass of the N-substituted carbamate.

[0140] As the catalyst, for example, Lewis acids and transition metal compounds that generate Lewis acids, organotin compounds, copper group metals, zinc, and various compounds of iron group metals can be used. Specifically, as the catalyst, Lewis acids and transition metal compounds represented by AlX3, TiX3, TiX4, VOX3, VX5, ZnX2, FeX3, SnX4 (where X is an oxygen atom, nitrogen atom, halogen atom, acetoxy group, alkoxy group, or aryloxy group, and has a valence that satisfies the metal oxidation number); organotin compounds represented by (CH3)3SnOCOCH3, (C2H5)SnOCOC6H5, Bu3SnOCOCH3, Ph3SnOCOCH3, Bu2Sn(OCOCH3)2, Bu2Sn(OCOC 11 H 23 )2, Ph3SnOCH3, (C2H5)3SnOPh, Bu2Sn(OCH3)2, Bu2Sn(OC2H5)2, Bu2Sn(OPh)2, Ph2Sn(CH3)2, (C2H5)3SnOH, PhSnOH, Bu2SnO, (C8H 17 )2SnO, Bu2SnCl2, BuSnO(OH), etc.; compounds of copper group metals such as CuCl, CuCl2, CuBr, CuBr2, CuI, CuI2, Cu(OAc)2, Cu(acac)2, copper oleate, Bu2Cu, (CH3O)2Cu, AgNO3, AgBr, silver picrate, AgC6H6ClO4, etc.; compounds of zinc such as Zn(acac)2; Fe(C 10Compounds of iron group metals such as H8)(CO)5, Fe(CO)5, Fe(C4H6)(CO)3, Co(mesitylene)2(PEt2Ph2), CoC5F5(CO)7, ferrocene, etc. (In the above, Bu represents a butyl group, Ph represents a phenyl group, and acac represents an acetylacetone chelate ligand.), amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine, and triethylamine, etc. can be mentioned. Among them, organometallic catalysts such as dibutyltin dilaurate, lead octylate, and stannaoctoate can be mentioned. These compounds may be used alone or as a mixture of two or more. It is also preferable to support the above-mentioned metal components on a carrier that is substantially inert and does not inhibit the reaction. As the carrier, various materials such as activated carbon, silicon, aluminum, zirconium, titanium, and their oxides and composite oxides are used.

[0141] The shape of the catalyst is preferably various shapes such as powder, columnar, ring-shaped, spherical, etc., and columnar, ring-shaped, or spherical is particularly preferred.

[0142] However, when the catalyst is used in the above-mentioned step (1), the above-mentioned catalyst residue, etc. may be supplied to step (2). In the pyrolysis reaction of step (2), such catalyst residue, etc. may be present without any problem.

[0143] In the reaction for producing the N-substituted carbamate compound, a reactor that meets the appropriate conditions is selected. As the reactor, those similar to those exemplified in the above step (1) can be mentioned.

[0144] Further, depending on the purpose, a step of recovering the decomposition gas and performing distillation separation using the boiling point difference may be added. For example, International Publication No. 2013 / 111353 (Reference 1) discloses recovering isocyanate and hydroxy compound generated by a thermal decomposition reaction as gas-phase components and performing distillation separation in a multi-stage distillation column. When the multi-stage distillation column is a tray column, various tray columns having sieve trays, cascade trays, turbo grid trays, ripple trays, dual trays, etc. can be appropriately used. Also, in step (2), it is also one of the preferred embodiments to control the reaction conditions by appropriately refluxing as necessary.

[0145] When the multi-stage distillation column is a packed column, as the solid packing material provided in the packed column, packing materials generally used in distillation columns and absorption columns can be appropriately used. Specifically, preferred solid packing materials include, for example, Raschig rings, cascade mini rings, Lessing rings, spiral rings, ball rings, interlock saddles, Steedman packing, McMahon packing, Dixon packing, helix packing, coil packing, heat pipe packing, Mellapak, Sulzer packing, Goodroll packing, Flexipak, etc.

[0146] The internal fittings such as fillers are preferably inert to the decomposition products, and the materials are preferably SUS304, SUS316, SUS316L, generally silicon oxide (composition formula: SiO2), aluminum oxide (composition formula: Al2O3), and fluorocarbon (a compound having a repeating unit of -CHF- or -CF2-). Also, glass, ceramic, and fluororesin containing these as constituent components are also preferred. In the case of glass and ceramic, the contents of silicon oxide and aluminum oxide are not particularly limited, and those in which the content of silicon oxide occupies 60% by mass or more or those in which the content of aluminum oxide occupies 60% by mass or more can be selected, and various materials can be selected.

[0147] As used herein, the term "ceramic" refers to a sintered body obtained by firing an inorganic substance. Here, regardless of whether it is a metal or a non-metal, it is a general term for inorganic solid materials such as molded bodies, powders, and films of semiconductors such as silicon, and inorganic compounds such as carbides, nitrides, borides, and titanium oxides. Examples of fluororesins include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, perfluoroalkoxy fluororesin, ethylene tetrafluoride - hexafluoropropylene copolymer, ethylene - tetrafluoroethylene copolymer, ethylene - chlorotrifluoroethylene copolymer, and the like. The preferred fillers shown here may contain other metal atoms as long as they do not conflict with the gist of the present embodiment.

[0148] <Step (3): Isocyanate Compound Concentration Step> In step (3), the isocyanate compound and the aprotic solvent are separated from the reaction solution containing the isocyanate compound obtained in step (2). By separating the excessively contained aprotic solvent, the amount of the reaction solution can be reduced, and by making the equipment for each step smaller, productivity can be improved and equipment costs can be reduced.

[0149] Step (3) can also be referred to as the isocyanate compound concentration step. The method for separating the aprotic solvent is not particularly limited, but from the viewpoints of productivity and ease of process design, known distillation separation is preferred.

[0150] From the viewpoint of suppressing side reactions, it is preferable to separate the aprotic solvent from the reaction solution containing the isocyanate compound under low-temperature conditions and for a short time as much as possible in the distillation separation in step (3). Therefore, step (3) is also preferably carried out by a continuous method, similar to the thermal decomposition reaction in step (2) above.

[0151] As a separation method by a continuous process, a reaction solution containing an isocyanate compound is continuously supplied to a reactor, and an aprotic solvent is continuously withdrawn from the reactor. Further, in the above-described step (2), it is preferable to use an aprotic solvent having a boiling point lower than that of the isocyanate compound. Thereby, the aprotic solvent can be withdrawn as a gas-phase component, and a fraction containing the isocyanate compound can be more efficiently separated as a liquid-phase component.

[0152] Alternatively, it is also a preferable embodiment to use an aprotic solvent having a boiling point higher than that of the isocyanate compound. Thereby, the aprotic solvent can be withdrawn as a liquid-phase component, and a fraction containing the isocyanate compound can be more efficiently separated as a gas-phase component.

[0153] The pressure in step (3) varies depending on the type of compound used and the reaction temperature, but any of reduced pressure, normal pressure, and increased pressure may be used as long as the separation of the isocyanate compound and the aprotic solvent is possible. The pressure can be set to the saturated vapor pressure of the aprotic solvent to be used, and it is preferably carried out in the range of 20 Pa or more and 1×10 6 Pa or less.

[0154] The operation time of step (3) (retention time in the case of the continuous method) is not particularly limited as long as separation of the isocyanate compound and the aprotic solvent is possible, but it is preferably 5 seconds or more and 100 hours or less, more preferably 10 seconds or more and 50 hours or less, even more preferably 20 seconds or more and 10 hours or less, still more preferably 20 seconds or more and 1 hour or less, even more preferably 20 seconds or more and 50 minutes or less, particularly preferably 20 seconds or more and 45 minutes or less, especially preferably 20 seconds or more and 40 minutes or less, more particularly preferably 30 seconds or more and 30 minutes or less, and most preferably 30 seconds or more and 25 minutes or less. When the operation time is at or below the above upper limit value, the operation time can be made shorter, and side reactions of the isocyanate compound can be more effectively suppressed. Also, when the operation time is at or above the above lower limit value, the aprotic solvent can be more sufficiently extracted into the gas phase.

[0155] The temperature of step (3) is not particularly limited as long as the isocyanate compound and the aprotic solvent are stable and separation of the isocyanate compound and the aprotic solvent is possible. However, since the isocyanate compound reacts at 100°C or higher and 130°C or lower to generate uretdione, it is preferable to separate from the aprotic solvent under low-temperature conditions and for a short time as much as possible. From the viewpoint of suppressing modification of the isocyanate compound, the temperature is preferably 300°C or lower, more preferably in the range of 20°C or higher and 290°C or lower, and even more preferably in the range of 30°C or higher and 280°C or lower.

[0156] There is no particular limitation on the form of separation. However, in order to efficiently recover the gas-phase components, it is preferable to use a known distillation apparatus. As such a distillation apparatus, for example, any of a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin-film evaporator, a reactor equipped with a support inside, a forced-circulation reactor, a falling-film evaporator, and a falling-drop evaporator, and a method using a combination thereof and the like, various known methods are used. From the viewpoint of quickly removing the aprotic solvent from the reaction system, a method using a distillation column, a multi-stage distillation column, a continuous multi-stage distillation column, a packed column, a tubular reactor, a thin-film evaporator, a falling-film evaporator, or a falling-drop evaporator is preferable. Further, since the aprotic solvent can be quickly transferred to the gas phase, a separation form having a large gas-liquid contact area is preferable. When the multi-stage distillation column is a packed column, as the solid packing material provided in the packed column, the packing materials generally used in distillation columns and absorption columns as described in the above step (2) can be appropriately used. Specifically, preferable solid packing materials include, for example, Raschig rings, cascade mini rings, Mellapak, Sulzer packing, and Goodroll packing.

[0157] The material of the process equipment and the lines may be any known material as long as it does not have an adverse effect on isocyanate or the like. However, since it is inexpensive, SUS304, SUS316, SUS316L, etc. can be preferably used.

[0158] In addition, in step (3), the above-described distillation separation may be performed once, or may be performed a plurality of times, i.e., two or more times. By performing it a plurality of times, the aprotic solvent can be removed to obtain a fraction containing a more concentrated isocyanate compound. The number of distillation times can be set to 1 or more and 5 or less, preferably 1 or more and 4 or less, more preferably 2 or more and 3 or less, and even more preferably 2, in consideration of the balance between cost and production efficiency. Further, when distillation is employed in step (3), it is also a preferable embodiment to control the conditions by appropriately refluxing as necessary.

[0159] <Step (4): Isocyanate compound isolation step (purification step)> In step (4), components with a boiling point higher than that of the isocyanate compound (high-boiling components) are removed from the fraction containing the isocyanate compound obtained in step (3) to purify the isocyanate compound.

[0160] Step (4) can also be referred to as an isocyanate compound isolation step or a purification step. The purification method of the isocyanate compound is not particularly limited, but from the viewpoints of productivity and ease of process design, known distillation separation is preferred.

[0161] From the viewpoint of suppressing side reactions, in the distillation separation in step (4), it is preferable to remove high-boiling components from the fraction containing the isocyanate compound and purify the isocyanate compound under low-temperature conditions and for a short time as much as possible. Therefore, step (4) is also preferably carried out by a continuous method similar to the thermal decomposition reaction in step (2) above.

[0162] As a separation method by a continuous method, a method is to continuously supply a fraction containing the isocyanate compound to a reactor and continuously extract the isocyanate compound from the reactor.

[0163] In addition, the fraction containing the isocyanate compound contains high-boiling components with a boiling point higher than that of the isocyanate compound, but it preferably contains, based on the mass of the fraction containing the isocyanate compound, 1 mass ppm or more and 50 mass% or less of a carbonyl compound represented by the following general formula (I) (hereinafter, may be referred to as "carbonyl compound (I)") as a high-boiling component.

[0164] By purifying the isocyanate compound in step (4) in the presence of the specific amount of the carbonyl compound (I) as a high-boiling component, the carbonyl compound (I) serves as a solvent with a boiling point higher than that of the isocyanate compound (hereinafter, may be referred to as "high-boiling solvent"), and the isocyanate compound can be extracted from the reactor as a gas-phase component and more efficiently isolated and purified. On the other hand, the high-boiling solvent remains at the bottom of the reactor as a liquid-phase component.

[0165] The content of the carbonyl compound (I) is preferably 1 mass ppm or more and 50 mass% or less, more preferably 10 mass ppm or more and 30 mass% or less, still more preferably 0.01 mass% or more and 15 mass% or less, and particularly preferably 1 mass% or more and 10 mass% or less, based on the mass of the fraction containing the isocyanate compound. When the content of the carbonyl compound (I) is at least the above lower limit value, the yield of the isocyanate compound can be further improved. On the other hand, when it is at most the above upper limit value, the amount of the reaction liquid can be further reduced, and the facilities for each step can be made smaller, thereby improving productivity and further reducing equipment costs.

[0166] [Chemical formula]

[0167] (In the general formula (I), R 11 is an organic group having a valence of (n11 + n12), and R 12 is a monovalent organic group. n11 is an integer of 1 or more and 8 or less, n12 is an integer of 0 or more and 7 or less, and the sum of n11 and n12 is 2 or more and 8 or less.)

[0168] The pressure in step (4) varies depending on the type of the compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure as long as the separation of the isocyanate compound and the high-boiling components is possible. The pressure can be set to the saturated vapor pressure of the isocyanate compound, and it is preferably carried out in the range of 20 Pa or more and 1×10 6 Pa or less.

[0169] The operation time of step (4) (retention time in the case of the continuous method) is not particularly limited as long as separation of the isocyanate compound and the high-boiling components is possible, but it is preferably 5 seconds or more and 100 hours or less, more preferably 10 seconds or more and 50 hours or less, even more preferably 20 seconds or more and 10 hours or less, still more preferably 20 seconds or more and 1 hour or less, even more preferably 20 seconds or more and 30 minutes or less, particularly preferably 20 seconds or more and 25 minutes or less, especially preferably 20 seconds or more and 20 minutes or less, more particularly preferably 30 seconds or more and 15 minutes or less, and most preferably 30 seconds or more and 10 minutes or less. By the operation time being below the above upper limit value, the operation time can be made shorter, and side reactions of the isocyanate compound can be more suppressed. Further, by the operation time being above the above lower limit value, the isocyanate compound can be more sufficiently extracted into the gas phase.

[0170] The temperature of step (4) is not particularly limited as long as the isocyanate compound and the high-boiling components are stable and separation of the isocyanate compound and the high-boiling components is possible. However, since the isocyanate compound reacts at 100°C or higher and 130°C or lower to generate uretdione, it is preferable to separate from the aprotic solvent under low-temperature conditions and for a short time as much as possible. From the viewpoint of suppressing modification of the isocyanate compound, the temperature is preferably 250°C or lower, more preferably in the range of 20°C or higher and 240°C or lower, and even more preferably in the range of 30°C or higher and 230°C or lower.

[0171] There is no particular limitation on the type of the isolation device, but in order to efficiently recover the gas-phase components, it is preferable to use a known distillation device. As such a distillation device, for example, any of a distillation column, a multi-stage distillation column, a multi-tubular reactor, a continuous multi-stage distillation column, a packed column, a thin-film evaporator, a reactor equipped with a support inside, a forced-circulation reactor, a falling-film evaporator, a falling-drop evaporator, and a method using a reactor including any of these, and a method combining these, etc., various known methods are used. From the viewpoint of quickly removing the isocyanate compound from the reaction system, a method using a distillation column, a multi-stage distillation column, a tubular reactor, a continuous multi-stage distillation column, a packed column, a thin-film evaporator, a falling-film evaporator is preferable, and a method using a distillation column, a multi-stage distillation column, a tubular thin-film evaporator, a thin-film evaporator or a tubular falling-film evaporator, etc. is more preferable. Further, since the isocyanate compound can be quickly transferred to the gas phase, a reactor having a large gas-liquid contact area structure is preferable.

[0172] The material of the isolation device and the line may be any known material as long as it does not have an adverse effect on isocyanates, etc., but since it is inexpensive, SUS304, SUS316, SUS316L, etc. can be preferably used.

[0173] Further, from the reaction solution containing the isocyanate compound obtained in the step (2), a component having a boiling point higher than that of the isocyanate compound is separated first, and a component containing the isocyanate compound is recovered in a step (3'), and the isocyanate compound and the aprotic solvent are separated from the component containing the isocyanate compound obtained in the step (3') to purify the isocyanate compound in a step (4'). Thus, the order of the components to be separated in the step (3) and the step (4) can also be changed. In the step (3'), the same operation as in the step (4) is performed, and in the step (4'), the same operation as in the step (3) is performed. Further, in the step (4), it is also one of the preferable embodiments to control the conditions by appropriately refluxing as necessary.

[0174] <Step (5): Primary amine compound and hydroxy compound regeneration step> In addition to the above-described steps (1) to (4), the manufacturing method of the present embodiment preferably further includes the following step (5). Step (5): Hydrolyzing a fraction containing an aprotic solvent separated in step (3) or a component having a boiling point higher than that of the isocyanate compound removed in step (4) (high-boiling component) in the coexistence of an alkali and water to obtain the primary amine compound and the hydroxy compound.

[0175] When the aprotic solvent has a boiling point higher than that of the isocyanate compound, the fraction containing the aprotic solvent separated in step (3) may contain a high-boiling component.

[0176] The high-boiling component includes the above-mentioned carbonyl compound (I) presumed to be produced by the reaction of the isocyanate compound and the aprotic solvent, and a polymer having one or more bonds selected from the group consisting of biuret bonds, allophanate bonds, isocyanurate bonds, urea bonds, carbodiimide bonds, uretonimine bonds, and imino trimer bonds. By hydrolyzing the high-boiling component containing these under alkaline conditions, the primary amine compound and the hydroxy compound used in step (1) can be obtained. Therefore, step (5) can also be referred to as a primary amine compound and hydroxy compound regeneration step.

[0177] Before performing the hydrolysis reaction, the hydroxy compound may be premixed with the high-boiling component. Since the hydroxy compound tends to have high solubility in the high-boiling component, by dissolving the high-boiling component in the hydroxy compound in advance, the reaction system can be made uniform and the reaction can proceed rapidly.

[0178] In addition, by supplying and mixing the hydroxy compound to the high-boiling component in advance, denaturation of various compounds contained in the high-boiling component can be further suppressed and the liquid phase state can be maintained.

[0179] Also, when separating the obtained primary amine compound and hydroxy compound after the hydrolysis reaction, generally, when the primary amine compound and water are mixed, they may be in a miscible state, and there is a risk that phase separation becomes difficult. However, by adding the hydroxy compound to the high-boiling components in advance, it becomes easier to phase-separate the primary amine compound and water.

[0180] Also, when purifying the primary amine compound and hydroxy compound by distillation separation after the hydrolysis reaction, there is a risk that the alkali used may precipitate in the distillation column and distillation cannot be significantly carried out. However, by adding the hydroxy compound to the high-boiling components in advance, the state in which the alkali is dissolved can be maintained, and continuous distillation separation can be carried out.

[0181] From the viewpoint of dissolving the high-boiling components and maintaining the liquid phase state, when the high-boiling components recovered as the liquid phase component in step (4) contain a hydroxy compound, the liquid phase component may be directly used in the hydrolysis reaction in step (5). Alternatively, a pipe for supplying the hydroxy compound may be provided in a pipe for recovering the high-boiling components continuously withdrawn as the liquid phase component from the reactor in step (4) to add the hydroxy compound.

[0182] The content of the hydroxy compound is preferably 20% by mass or more and 300% by mass or less, more preferably 50% by mass or more and 150% by mass or less, based on the total mass of the fraction containing the aprotic solvent separated in step (3) and the components having a boiling point higher than that of the isocyanate compound removed in step (4). When the content of the hydroxy compound is within the above range, the reaction system in step (5) can be made uniform and the reaction can proceed rapidly.

[0183] When transferring the high-boiling components from the reactor in step (4) to the reactor in step (5), it is preferable to transfer the high-boiling components while maintaining them in a liquid state. Therefore, the high-boiling components are supplied to the reactor in step (5) while being maintained at preferably 50°C or higher and 300°C or lower, more preferably 100°C or higher and 260°C or lower.

[0184] The amount of water used (in molar amount) is preferably 1.0 times or more and 200 times or less, more preferably 5 times or more and 150 times or less, and even more preferably 5 times or more and 100 times or less in a stoichiometric ratio with respect to the total molar amount of isocyanate groups, biuret bonds, allophanate bonds, isocyanurate bonds, carbamate bonds, and urea bonds contained in the high-boiling components. When the amount of water used is equal to or less than the above upper limit value, undesirable reactions caused by an acidic atmosphere associated with an increase in the ionic product caused by a large amount of high-temperature and high-pressure water, for example, the formation of imine compounds, which are by-products internally cyclized by the deammoniation reaction of primary amine compounds, can be more effectively suppressed. In addition, the energy load in the subsequent dehydration process can be further reduced, and it is possible to suppress the energy consumption in production and miniaturize the apparatus. On the other hand, when the amount of water used is equal to or more than the above lower limit value, the decomposition reaction of the high-boiling components proceeds more favorably.

[0185] In addition, since the amount of water used varies depending on the composition of the bonds contained in the high-boiling components and their hydrolyzability, it changes depending on the composition of the object to be decomposed, but efficient decomposition is possible generally within the above range.

[0186] Furthermore, when the reaction can be efficiently carried out by using an alkali or the like, the amount of water can be further reduced. When the decomposition efficiency decreases, crosslinkable bonds typified by urea bonds, which can be generated as intermediates of the hydrolysis reaction, increase, and high molecular weight substances, that is, gels, may be formed in the system. Gels become scale, adhere to the inside of the apparatus, not only significantly reduce the reaction efficiency but also require cleaning of the apparatus, which is a factor reducing the economic efficiency. However, by setting the amount of water used within the above range, the decomposition proceeds more favorably, scale generation inside the apparatus can be more effectively suppressed, and thus the primary amine compound can be efficiently recovered.

[0187] The alkali is not particularly limited, and examples thereof include hydroxides and oxides of alkali metals and alkaline earth metals such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, magnesium oxide, calcium oxide, and barium oxide; heterocyclic compounds and tertiary amines such as pyridine, methylpyridine (including isomers), dipropylethylamine, N-methylmorpholine, N-ethylmorpholine, triethylamine, and triethylenediamine. These alkalis can be used alone or in combination of two or more. Among them, as the alkali, hydroxides and oxides of alkali metals and alkaline earth metals are preferable, and hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide are more preferable.

[0188] Further, as the shape of the alkali, the alkali may be uniformly miscible with the reaction solution or may be non-uniform. It is preferable to use a uniform alkali, which can accelerate the decomposition reaction in the reactor, contribute to the suppression of by-product formation, and further improve the yield.

[0189] The amount of alkali used (molar amount) can be 0.001 times or more and 10 times or less, preferably 0.01 times or more and 1 time or less, and more preferably 0.03 times or more and 0.5 times or less in a stoichiometric ratio with respect to the molar amount of isocyanate groups, biuret bonds, allophanate bonds, isocyanurate bonds, carbamate bonds, urea bonds, carbodiimide bonds, uretonimine bonds, iminotrimer bonds, free rearrangement ends, cyclized products of free rearrangement ends, and oxycarbonylcarbamate bonds contained in the high-boiling components.

[0190] When no alkali is used, the decomposition of the high-boiling components is slow or does not occur, so the yield of the primary amine compound decreases. On the other hand, the bonds contained in the high-boiling components have different decomposabilities depending on the bonding mode, and it is possible to promote the decomposition of each bonding mode by appropriately selecting the type of alkali, the form of the reaction, etc.

[0191] For example, a free radical terminal, a cyclized product of a free radical terminal, an isocyanurate bond, and an imino trimer bond are generally less likely to undergo a decomposition reaction with water and less likely to produce a primary amine compound compared to a biuret bond, an allophanate bond, a carbamate bond, an oxycarbonyl carbamate bond, a urea bond, a carbodiimide bond, and a uretonimine bond. In particular, an isocyanurate bond and an imino trimer bond have poor hydrolyzability, and it is known that the progress of decomposition is slow by known methods. When these bonds are crosslinking bonds and remain in the reaction solution as high molecular weight substances, when separating a primary amine compound or a hydroxy compound from the reaction solution, blockage in the apparatus may occur due to precipitation or the like, or the amount of the primary amine compound that can be recovered decreases.

[0192] On the other hand, when using a high-boiling component, a hydroxy compound, water, and an alkali, the decomposition of the above-described various bonds is promoted, and a high molecular weight substance does not remain in the reaction solution. Therefore, when separating a primary amine compound or a hydroxy compound from the reaction solution, blockage in the apparatus due to precipitation or the like can be avoided, so that the primary amine compound can be efficiently recovered.

[0193] The reaction temperature of hydrolysis in step (5) can be appropriately set according to the composition of the high-boiling components to be decomposed. However, considering the energy load in the hydrolysis reaction, a temperature range of 100°C or higher and 300°C or lower is preferred, a range of 160°C or higher and 300°C or lower is more preferred, and a range of 200°C or higher and 280°C or lower is even more preferred. When the reaction temperature is in the temperature range above the upper limit value, the decomposition efficiency is almost saturated. Rather, the environment of high-temperature and high-pressure water becomes a reaction field where the ionic product increases and the acidity is improved. Therefore, unfavorable reactions may occur. For example, the formation of imine compounds, which are by-products internally cyclized by the deammoniation reaction of primary amine compounds, can be cited. On the other hand, when the temperature is in the range below the lower limit value, the decomposition efficiency decreases, increasing the crosslinkable bonds typified by urea bonds that can be generated as intermediates in the hydrolysis reaction, and high molecular weight substances, that is, gels, may be produced in the system. Gels become scale and adhere to the inside of the apparatus, not only significantly reducing the reaction efficiency but also requiring the cleaning of the apparatus, which is a factor reducing the economic efficiency. However, when the reaction temperature is within the above range, the decomposition of crosslinkable molecules typified by urea bonds proceeds more favorably, and the generation of scale inside the apparatus can be more suppressed. Therefore, while maintaining continuous operability, the primary amine compound can be recovered more efficiently.

[0194] The reaction pressure can be 0.01 kPa or higher and 10 MPa (absolute pressure) or lower, and the reaction can be carried out under reduced pressure, normal pressure, or increased pressure. The reaction time (residence time in the case of continuous reaction) can be 0.01 hour or longer and 100 hours or shorter. The reaction solution can be appropriately sampled to measure the production amount of the target compound, the primary amine compound, and the reaction can be terminated when the desired production amount is reached.

[0195] In the hydrolysis reaction in step (5), low-boiling components with a boiling point of 30°C or lower may be generated. However, the pressure in the reaction system may increase due to these low-boiling components, or the reaction may be slowed down due to the presence of low-boiling components. Therefore, it is preferable to carry out the hydrolysis reaction while extracting at least a part of the low-boiling components as gas-phase components outside the reaction system. In that case, it is preferable to prevent water from being extracted outside the reaction system together with the low-boiling components, such as by providing a condenser in the middle of the line for extracting the low-boiling components from the reactor where the hydrolysis reaction is carried out. In addition, carbon dioxide may be generated by the reaction of isocyanate groups, biuret bonds, allophanate bonds, isocyanurate bonds, carbamate bonds, urea bonds, carbodiimide bonds, uretonimine bonds, iminotrimer bonds, free Schiffs rearrangement ends, cyclized products of free Schiffs rearrangement ends, and oxycarbonylcarbamate bonds with water, and it is preferable to extract the generated carbon dioxide outside the reaction system.

[0196] The generated carbon dioxide may slow down the hydrolysis reaction because it forms a primary amine compound and a carbonate produced by the hydrolysis reaction. The ease of formation of the carbonate depends on the nucleophilicity of the primary amine compound, and the order of carbonate formation is generally aliphatic amines ≥ substituted cycloaliphatic polyamines > aromatic amines. Therefore, it is preferable to adjust the amount of the generated carbon dioxide extracted outside the reaction system as needed according to the structure of the primary amine compound.

[0197] The reactor for carrying out the hydrolysis reaction in step (5) is not particularly limited, and known reactors can be used. For example, a stirred tank, a pressurized stirred tank, a vacuum stirred tank, a tower reactor, a distillation column, a packed column, a thin film evaporator, a paddle dryer equipped with a forced conveyance device, an extruder equipped with a degassing function, a vertical thin film evaporator equipped with a forced conveyance device, a tubular reactor, etc. Depending on the reaction method and conditions, conventionally known reactors can be appropriately combined and used. Further, the reaction may be batchwise or continuous flow type, and the reaction apparatus may be selected according to each reaction form. There is also no particular limitation on the material of the reactor, and known materials can be used. For example, those made of glass, stainless steel, carbon steel, Hastelloy, those with a glass lining on the base material, those with a Teflon (registered trademark) coating, etc. can be used. SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, instrumentation devices such as a flow meter and a thermometer, a mechanism for maintaining pressure, and known process devices such as a reboiler, a pump, and a condenser may be added. Heating may be by known methods such as steam and a heater, and cooling can also use known methods such as natural cooling, cooling water, and brine.

[0198] From the reaction solution obtained by the hydrolysis reaction, the primary amine compound can be recovered through known separation methods such as distillation separation, liquid-liquid separation, solid-liquid separation, and membrane separation. The recovered primary amine compound is preferably reused as a raw material in step (1) described above. Further, it is also preferable to recover the hydroxy compound generated by the reaction of the high-boiling components and water and reuse it as a raw material in step (1).

[0199] The method for recovering the primary amine compound and the hydroxy compound preferably includes the following steps (5a) to (5d), and these steps can be carried out continuously, or steps (5a) to (5d) can also be carried out simultaneously. Further, for example, the operations of steps (5c) to (5d) can also be carried out before the operations of steps (5a) to (5b), and some steps can be interchanged and carried out.

[0200] [Step (5a): Separation of primary amine compound] In step (5a), the primary amine compound is separated from the reaction solution after the hydrolysis reaction. As the method for separating the primary amine compound, known methods can be used, for example, distillation separation, liquid-liquid separation, solid-liquid separation, membrane separation, etc. In step (5a), the primary amine compound can also be continuously separated from the liquid-phase component (reaction solution) continuously discharged in the above step (5).

[0201] [Step (5b): Purification of primary amine compound] In step (5b), the primary amine compound separated in the above step (5a) is purified. As the method for purifying the primary amine compound, known methods can be used, for example, distillation separation, liquid-liquid separation, solid-liquid separation, membrane separation, etc. In step (5b), the primary amine compound continuously separated in step (5a) can also be continuously purified.

[0202] [Step (5c): Separation of hydroxy compound] In step (5c), the hydroxy compound used as a raw material in the above step (1) is separated from the reaction solution after the hydrolysis reaction. As the method for separating the hydroxy compound, known methods can be used, for example, distillation separation, liquid-liquid separation, solid-liquid separation, membrane separation, etc. In step (5c), the hydroxy compound can also be continuously separated from the gas-phase component continuously discharged in the above step (5).

[0203] [Step (5d): Purification of hydroxy compound] In step (5d), the hydroxy compound separated in the above step (5c) is purified. As the method for purifying the hydroxy compound, known methods can be used, for example, distillation separation, liquid-liquid separation, solid-liquid separation, membrane separation, etc. In step (5d), the hydroxy compound continuously separated in step (5c) can also be continuously purified.

[0204] The primary amine compound and the hydroxy compound recovered by the above recovery method can be reused in the above step (1) respectively. That is, it is preferable that the manufacturing method of the present embodiment further includes the following step (7). Step (7) of reusing the primary amine compound and the hydroxy compound recovered in the above step (5) in the above step (1).

[0205] [Step (7): Recycling step of primary amine compound and hydroxy compound] In step (7), the primary amine compound and the hydroxy compound recovered in step (5) are reused in the above step (1). At that time, since there is a risk of affecting the production of the N-substituted carbamate compound in the above step (1) and the quality of the obtained N-substituted carbamate compound and the isocyanate compound obtained in the subsequent steps, in the above step (5) (specifically, the above step (5b) and the above step (5d)), it is preferable to distill and recover the primary amine compound and the hydroxy compound so that the content of the metal component is 1000 mass ppm or less and the content of the halogen atom is 1000 mass ppm or less with respect to the total mass of the primary amine compound.

[0206] In addition, the hydroxy compound can also be reused in the above step (5) for pre-mixing with high-boiling components.

[0207] [Other steps] The manufacturing method of the present embodiment can further include other steps in addition to the above-described steps (1) to (5).

[0208] [Step (1a): N-substituted carbamate compound concentration step] In step (1a), the N-substituted carbamate compound obtained in step (1) is concentrated. That is, step (1a) can also be referred to as an N-substituted carbamate compound concentration step. The method for concentrating the N-substituted carbamate compound is not particularly limited, but from the viewpoints of productivity and ease of process design, known distillation separation is preferable.

[0209] In the distillation separation in step (1a), from the viewpoint of suppressing side reactions, it is preferable to remove unreacted raw material components such as hydroxy compounds from the reaction solution containing the N-substituted carbamate compound at as low a temperature as possible and for as short a time as possible to concentrate the N-substituted carbamate compound. Therefore, step (1a) is also preferably carried out by a continuous method in the same manner as the reaction in step (1) above.

[0210] As a concentration method by a continuous method, a method is adopted in which a reaction solution containing an N-substituted carbamate compound is continuously supplied to a reactor, and the concentrated N-substituted carbamate compound is continuously withdrawn from the reactor. The supply rate of the above-mentioned reaction solution to the reactor and the withdrawal rate of the N-substituted carbamate compound can be appropriately adjusted according to the degree of concentration of the N-substituted carbamate compound.

[0211] Also, in step (1a), after premixing the aprotic solvent used in the subsequent step (1), the above-mentioned concentration may be carried out. As the aprotic solvent used at this time, it is preferable to use one having a boiling point higher than that of the hydroxy compound. Thereby, it is possible to further prevent liquid depletion due to concentration.

[0212] [Step (6): Solvent recovery step (solvent reuse step)] In step (6), the hydroxy compound withdrawn in step (2) is circulated to step (1) for reuse, and the aprotic solvent separated in step (3) is circulated to step (2) for reuse. That is, step (6) can be referred to as a solvent recovery step or a solvent reuse step.

[0213] The hydroxy compound withdrawn in step (2) and the aprotic solvent separated in step (3) may be separately separated and purified to recover the hydroxy compound and the aprotic solvent respectively. Alternatively, the components withdrawn in these steps may be combined and mixed, and then separated and purified to recover the hydroxy compound and the aprotic solvent.

[0214] For the separation and purification of hydroxy compounds and aprotic solvents, known methods can be used, such as distillation separation, liquid-liquid separation, solid-liquid separation, membrane separation, etc. As the distillation separation method, for example, a method including any one of a multi-stage distillation column, a tray column, a packed column, a thin-film evaporator, a falling-film evaporator, a falling-drop evaporator, and a falling-film type evaporator with a forelimb is used. In step (6), hydroxy compounds and aprotic solvents can be continuously separated from the gas-phase components continuously discharged in step (2) and the gas-phase components continuously discharged in (3), respectively. Also, it is one of the preferred embodiments to control the conditions by appropriately refluxing as necessary.

[0215] In addition, regarding the separation and purification after collecting and mixing the components extracted in each step, when distillation separation is employed, due to the difference in boiling points, it is preferable to recover the hydroxy compound from the top of the column and recover the aprotic solvent as a side-cut fraction from the middle stage.

[0216] Also, the recovered hydroxy compound can be reused for premixing with high-boiling components in step (5) and can also be reused as a raw material for step (1).

[0217] <Raw Materials and Products> The raw materials and products (including intermediate products) used in the method for producing the isocyanate compound of this embodiment will be described in detail below.

[0218] [Primary Amine Compound] Examples of the primary amine compound include compounds represented by the following general formula (II) (hereinafter sometimes referred to as "primary amine compound (II)"), etc.

[0219] [Chemical Formula]

[0220] (In general formula (II), R 21is an n21-valent organic group. n21 is an integer of 2 or more. )

[0221] (R 21 ) R 21 is an n21-valent organic group, preferably an organic group having 3 or more and 85 or less carbon atoms, more preferably an organic group having 3 or more and 30 or less carbon atoms.

[0222] R 21 The organic group in is an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a group formed by bonding an aliphatic hydrocarbon group and an aromatic hydrocarbon group. Specific R 21 includes, for example, a cyclic hydrocarbon group, an acyclic hydrocarbon group, a group in which an acyclic hydrocarbon group is bonded to one or more cyclic groups, and a group in which these groups are covalently bonded to a specific non-metal atom. Examples of the cyclic group include a cyclic hydrocarbon group, a heterocyclic group, a heterocyclic spiro group, a heterobridged ring group, etc. Examples of the cyclic hydrocarbon group include a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, a ring assembly hydrocarbon group, a cyclic hydrocarbon group having a side chain, etc. Examples of the non-metal atom include carbon, oxygen, nitrogen, sulfur, silicon, etc.

[0223] Note that "covalently bonded to a specific non-metal atom" means, for example, a state in which the above-exemplified group is covalently bonded to a group represented by the following formulas (II)-1a to (II)-1p.

[0224]

Chemical formula

[0225] Among them, the organic group in R 21 is preferably a cyclic hydrocarbon group, an acyclic hydrocarbon group, a group in which an acyclic hydrocarbon group is bonded to one or more cyclic groups, or a group in which these groups are covalently bonded to a group represented by formula (II)-1a, formula (II)-1b, formula (II)-1c, formula (II)-1e, or formula (II)-1j.

[0226] R 21 When R is an aliphatic hydrocarbon group, specific examples of the primary amine compound (II) include aliphatic diamines, aliphatic triamines, substituted cycloaliphatic polyamines, and the like.

[0227] Examples of the aliphatic diamines include ethylenediamine, diaminopropane (each isomer), diaminobutane (each isomer), diaminopentane (each isomer), diaminohexane (each isomer), diaminodecane (each isomer), and the like.

[0228] Examples of the aliphatic triamines include triaminohexane (each isomer), triaminononane (each isomer), triaminodecane (each isomer), triaminoundecane (each isomer), 4-aminomethyl-1,8-octanediamine, and the like.

[0229] Examples of the substituted cycloaliphatic polyamines include diaminocyclobutane (each isomer), diaminocyclohexane (each isomer), 3-aminomethyl-3,5,5-trimethylcyclohexylamine (at least one isomer of the cis and trans isomers), methylenebis(cyclohexylamine) (each isomer), and the like.

[0230] R 21 When R is an aromatic group, specific examples of the primary amine compound (II) include aromatic diamines, aromatic triamines, and the like.

[0231] Examples of aromatic diamines include diaminobenzene (each isomer), diaminotoluene (each isomer), methylenedianiline (each isomer), diaminomesitylene (each isomer), diaminobiphenyl (each isomer), diaminodibenzyl (each isomer), bis(aminophenyl)propane (each isomer), bis(aminophenyl)ether (each isomer), bis(aminophenoxyethane) (each isomer), diaminoxylene (each isomer), diaminoanisole (each isomer), diaminophenetole (each isomer), diaminonaphthalene (each isomer), diaminomethylbenzene (each isomer), diaminomethylpyridine (each isomer), diaminomethylnaphthalene (each isomer), diaminodiphenylmethane (each isomer), tetramethylxylylenediamine (each isomer), etc.

[0232] Examples of aromatic triamines include triaminobenzene (each isomer), triaminomethylbenzene (each isomer), tris(aminopropan-yl)benzene (each isomer), tris(aminopropan-yl)-methylbenzene (each isomer), tris(aminomethyl)-methylbenzene (each isomer), ((aminophenylene)bis(methylene))bis(aminebenzene) (each isomer), etc.

[0233] R 21When the aliphatic hydrocarbon group or aromatic group in [compound] has 1 to 4 ester groups, as the primary amine compound (II), specifically, for example, an amine compound having an ester group obtained by reacting the carboxy group of an amino acid with a hydroxy compound is preferred. Specific examples of such an amine compound having an ester group include, for example, 2-aminoethyl acrylate, 2-aminoethyl 2-methylacrylate, 2-aminopropyl acrylate, 2-aminopropyl 2-methylacrylate, 3-aminopropyl acrylate, 3-aminopropyl 2-methylacrylate, 4-aminobutyl acrylate, 4-aminobutyl 2-methylacrylate, 5-aminopentyl acrylate, 5-aminopentyl 2-methylacrylate, 6-aminohexyl acrylate, 6-aminohexyl 2-methylacrylate, 8-aminooctyl acrylate, 8-aminooctyl 2-methylacrylate, 10-aminodecyl acrylate, 10-aminodecyl 2-methylacrylate, 11-aminoundecyl acrylate, 11-aminoundecyl 2-methylacrylate, 12-aminododecyl acrylate, 12-aminododecyl 2-methylacrylate, lysine methyl ester diamine, lysine ethyl ester diamine, 2-aminoethyl 2,5-diaminopentanoate, 2-aminoethyl 2,6-diaminohexanoate, bis(2-aminoethyl) 2-aminobutanedioate, bis(2-aminoethyl) 2-aminopentanedioate, tris(2-aminoethyl) hexane-1,3,6-tricarboxylate, and the like.

[0234] R 21When the aliphatic hydrocarbon group or aromatic group has 1 to 4 nitrogen atoms, as the primary amine compound (II), specifically, for example, an amine compound having 1 to 4 secondary or tertiary amines other than the terminal of the aliphatic hydrocarbon group or aromatic group is preferable. Specific examples of the amine compound having 1 to 4 secondary or tertiary amines other than the terminal of the aliphatic hydrocarbon group or aromatic group mentioned here include, for example, 2-(dimethylamino)ethylamine, 2-(diethylamino)ethylamine, 2-(diisopropylamino)ethylamine, 2-(cyclohexylamino)ethylamine, 3-(cyclohexylamino)propylamine, 3-(diethylamino)propylamine, 3-(dimethylamino)propylamine, diethylenetriamine, diisopropyltriamine, bis-(3-aminopropyl)methylenamine, 3-(2-aminoethylamino)propylamine, N,N'-bis(3-aminopropyl)ethylenediamine, 1-(3-aminopropyl)imidazole, trisaminoethylamine, trisaminopropylamine and the like.

[0235] (n21) n21 represents the number of amino groups and is an integer of 2 or more, preferably an integer of 2 to 10, more preferably an integer of 3 or more, and still more preferably 3.

[0236] Among these, as the primary amine compound (II), diaminohexane (each isomer), 4-aminomethyl-1,8-octanediamine, triaminohexane (each isomer), triaminoundecane (each isomer), 3-aminomethyl-3,5,5-trimethylcyclohexylamine, methylenebis(cyclohexylamine) (each isomer), diaminoxylene (each isomer), methylenedianiline (each isomer), triaminobenzene (each isomer), triaminomethylbenzene (each isomer), or tris(aminopropan-yl)-methylbenzene (each isomer) is preferable.

[0237] As the primary amine compound (II), amino acid derivatives are also preferably used. As used herein, an amino acid derivative means a compound synthesized from an amino acid as a raw material. As will be described later, the amino acid may be a natural amino acid or a synthetic amino acid. Further, the derivative may be a simple derivative or in the form of an inorganic acid salt.

[0238] Preferred amino acid derivatives include, for example, compounds represented by the following general formula (II-1) or (II-2) (hereinafter, may be abbreviated as "amino acid derivative (II-1)" etc. respectively).

[0239]

Chemical formula

[0240] In general formula (II-1), R 211 is a divalent or trivalent organic group, and is the same as the above R 21 . Among them, R 211 is preferably a structure obtained by removing the -NHCOOH group from an amino acid, and is more preferably an aliphatic hydrocarbon group having 1 or more carbon atoms or an aromatic group having 6 or more carbon atoms, which may contain a primary amino group, a sulfur atom, an oxygen atom, or a halogen atom, and is even more preferably a divalent or trivalent aliphatic hydrocarbon group having 1 to 15 carbon atoms or a divalent or trivalent aromatic group having 6 to 15 carbon atoms.

[0241] In general formula (II-1), X 211 is an oxygen atom or a secondary amino group (-NH-). Among them, X 211 is preferably an oxygen atom.

[0242] In general formula (II-1), R 212 is a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, an aromatic group having 6 to 15 carbon atoms, or a hydrogen atom. Among them, R 212 is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.

[0243] n211 is an integer of 2 or more, and among them, n211 is preferably 2 or 3.

[0244] In the case of α-amino acids, the bonding modes of amino groups, carboxy groups, etc. to the α-carbon can be stereochemically twofold, and are respectively distinguished as D-type and L-type optical isomers. The amino acid derivative may be D-type, L-type, or a mixture or racemate thereof. Many amino acids that can be obtained industrially at low cost are amino acids produced by fermentation, and most of them are L-type, but they can be preferably used. In the present specification, although the configuration is not shown, either D-type or L-type is shown.

[0245]

Chemical formula

[0246] In general formula (II-2), R 221 is an n221-valent organic group or a hydrogen atom, and when it is an n221-valent organic group, it is the same as the above R 21 . Among them, R 221 is preferably an aliphatic hydrocarbon group having 1 to 15 carbon atoms and 1 to 4 valences, or an aromatic group having 6 to 15 carbon atoms and 1 to 4 valences.

[0247] In general formula (II-2), X 221 is an oxygen atom or a secondary amino group (-NH-), and among them, an oxygen atom is preferable.

[0248] In general formula (II-2), n221 is an integer of 1 to 4.

[0249] In general formula (II-2), R 222 is a monovalent aliphatic hydrocarbon group, a monovalent aromatic group, or a hydrogen atom. Among them, R 222 is preferably a monovalent aliphatic hydrocarbon group having 1 or more carbon atoms or a monovalent aromatic group having 6 or more carbon atoms, which may contain one or more selected from the group consisting of a primary amino group, a sulfur atom, an oxygen atom, and a halogen atom, or a hydrogen atom. Moreover, it is more preferable that it is a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms or a monovalent aromatic group having 6 to 15 carbon atoms, which may contain one or more selected from the group consisting of a primary amino group, a sulfide bond, an ether bond, and a disulfide bond; a group having 7 to 15 carbon atoms, which may contain one or more selected from the group consisting of a primary amino group, a sulfide bond, an ether bond, and a disulfide bond, in which an aliphatic hydrocarbon group and an aromatic group are bonded; a group represented by the following general formula (II-2a) or (II-2b); or a hydrogen atom.

[0250]

Chemical formula

[0251] In general formula (II-2a), R 223 is a group represented by the following general formula (II-2c), (II-2d), or (II-2e), or a hydrocarbon group having 1 to 10 carbon atoms. In general formula (II-2a), n222 is an integer of 0 or more and 5 or less. In general formula (II-2a), the wavy line represents a bond.

[0252] In general formula (II-2b), R 224 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms. In general formula (II-2b), n223 is an integer of 0 or more and 5 or less. In general formula (II-2b), the wavy line represents a bond.

[0253]

Chemical formula

[0254] In general formula (II-2c), R 225 is a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a linear or branched alkylene group having 1 to 6 carbon atoms is preferable. In general formula (II-2d), n223 is an integer of 1 or more and 9 or less. In the general formula (II-2e), n224 is an integer of 0 or more and 9 or less. In the general formulas (II-2c) to (II-2e), the wavy line represents a bond.

[0255] As the amino acid derivative, an amino acid ester is preferable. Therefore, preferable amino acid derivatives (II-1) and (II-2) are exemplified as follows.

[0256] Preferable amino acid derivatives (II-1) specifically include compounds represented by the following general formulas (II-1-1) to (II-1-3).

[0257]

Chemical formula

[0258] In the general formulas (II-1-1) to (II-1-3), R 213 is the same as the above R 212 . Among them, R 213 is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms.

[0259] Preferable amino acid derivatives (II-2) include, for example, compounds represented by the general formulas (II-2-1) to (II-2-4).

[0260]

Chemical formula

[0261] In the general formulas (II-2-1) to (II-2-4), R 226 is a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms, a monovalent aromatic group having 6 to 15 carbon atoms, or a hydrogen atom. In the general formulas (II-2-1) to (II-2-4), R 227 is the same as R 222 .

[0262] As the amino acid derivative, a compound represented by the following general formula (II-3) (hereinafter, may be referred to as "amino acid derivative (II-3)") is also preferably used.

[0263]

Chemical formula

[0264] In the general formula (II-3), n231 is 1 or 2.

[0265] In the general formula (II-3), R 231 is an aliphatic hydrocarbon group having 1 to 15 carbon atoms or an aromatic group having 6 to 15 carbon atoms which may contain an ether bond or a sulfide bond, a group having 7 to 15 carbon atoms which may contain an ether bond or a sulfide bond and in which an aliphatic hydrocarbon group and an aromatic group are bonded, or a group represented by the general formula (II-2c), (II-2d), or (II-2e).

[0266] In the general formula (II-3), R 232 is a monovalent aliphatic hydrocarbon group having 1 to 15 carbon atoms or a monovalent aromatic group having 6 to 15 carbon atoms which may contain one or more selected from the group consisting of a primary amino group, a sulfide bond, an ether bond, and a disulfide bond, a group having 7 to 15 carbon atoms which may contain one or more selected from the group consisting of a primary amino group, a sulfide bond, an ether bond, and a disulfide bond and in which an aliphatic hydrocarbon group and an aromatic group are bonded, a group represented by the following general formula (II-2a) or (II-2b), or a hydrogen atom.

[0267] Preferred amino acid derivatives (II-3) include compounds represented by the following general formulas (II-3-1) to (II-3-39) and the like.

[0268]

Chemical formula

[0269]

Chemical formula

[0270] [Chemical formula]

[0271] In general formulas (II-3-1) to (II-3-39), R 3 and R 4 are each independently an aliphatic hydrocarbon group having 1 to 10 carbon atoms or a hydrogen atom. Among them, R 3 is preferably an alkyl group having 1 to 4 carbon atoms. R 4 is preferably an alkyl group having 1 to 6 carbon atoms.

[0272] In general formulas (II-3-1) to (II-3-39), R is a halogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. Among them, R is preferably a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.

[0273] In general formulas (II-3-1) to (II-3-39), n is an integer of 0 or more and 2 or less. Among them, n is preferably 1 or 2.

[0274] In general formulas (II-3-1) to (II-3-39), m and p are each independently an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 6 or less, and more preferably an integer of 1 or more and 3 or less.

[0275] Among these, as the amino acid derivative (II-3), compounds represented by the above general formulas (II-3-3), (II-3-4), (II-3-13), (II-3-14), (II-3-38), or (II-3-39) are preferred.

[0276] Among them, as the amino acid derivative (II-3), amino acid esters derived from a lysine backbone such as lysine methyl ester, lysine ethyl ester, lysine β-aminoethyl ester; amino acid esters derived from a glutamic acid backbone such as glutamic acid methyl ester, glutamic acid bis(β-aminoethyl) ester; amino acid esters derived from a methionine skeleton such as methionine methyl ester; amino acid esters derived from a glycine skeleton such as glycine methyl ester; amino acid esters derived from a phenylalanine skeleton such as phenylalanine methyl ester; amino acid esters derived from an aspartic acid skeleton such as aspartic acid methyl ester; amino acid esters derived from an alanine skeleton such as alanine methyl ester; amino acid esters derived from a leucine skeleton such as leucine methyl ester; amino acid esters derived from an isoleucine skeleton such as isoleucine methyl ester; and amino acid esters derived from a valine skeleton such as valine methyl ester are particularly preferred.

[0277] The above-mentioned amino acid esters can be produced, for example, by reacting an amino acid with a compound having an alcoholic hydroxy group in the presence of an inorganic acid, or by reacting an amino acid inorganic acid salt with an amino alcohol inorganic acid salt in the presence of an inorganic acid.

[0278] The inorganic acid may be any inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, boric acid, hydrofluoric acid, etc., but sulfuric acid, phosphoric acid, and hydrochloric acid are preferred, and hydrochloric acid is more preferred.

[0279] The amino acid ester may be used in the form of an inorganic acid salt. The amino acid ester inorganic acid salt is preferably formed by the above inorganic acid, and is preferably an amino acid ester sulfate, an amino acid ester phosphate, or an amino acid ester hydrochloride, and more preferably an amino acid ester hydrochloride.

[0280] The amino acid is preferably an aliphatic or aromatic amino acid having at least one amino group and at least one carboxy group and having 2 to 18 carbon atoms, or a lactam having a 3-membered ring or more and 12-membered ring or less.

[0281] The amino acid may be a natural amino acid or a synthetic amino acid.

[0282] Examples of natural amino acids include alanine, arginine, asparagine, glutamine, glutamic acid, glycine, histidine, isoleucine, leucine, lysine, aspartic acid, methionine, phenylalanine, tryptophan, valine, ornithine, and the like.

[0283] Synthetic amino acids can be produced by known methods. For example, they can be produced by Strecker synthesis using an aldehyde compound. Examples of aldehydes include compounds represented by the following general formula (A) (hereinafter sometimes abbreviated as "compound (A)").

[0284]

Chemical formula

[0285] In general formula (A), R a is a monovalent aliphatic hydrocarbon group having 1 or more carbon atoms or an aromatic group having 6 or more carbon atoms, which may contain an oxygen atom or a halogen atom. Among them, R a is preferably a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic group having 6 or more carbon atoms.

[0286] In general formula (A), a is an integer of 1 or more and 3 or less.

[0287] Examples of preferred compound (A) include acetaldehyde, propionaldehyde, hexyl aldehyde, octyl aldehyde, capric aldehyde, phenylacetaldehyde, benzaldehyde, dimethoxybenzaldehyde, chlorobenzaldehyde, fluorobenzaldehyde, heliotropin, cyclamen benzaldehyde, furfural, naphthaldehyde, phthalaldehyde, and the like. When these compounds have isomeric structures, the isomers are also included.

[0288] The amino acid inorganic acid salt is an inorganic acid salt of the amino acid. Particularly preferably used amino acids are aliphatic monoaminomonocarboxylic acids, diamino monocarboxylic acids, monoaminodicarboxylic acids, diamino dicarboxylic acids, etc. Lactams formed by cyclization of these amino acids are also preferably used.

[0289] Specific examples of the above compounds include glycine, 3-aminopropionic acid, ω-aminocaproic acid, ω-aminolauric acid, alanine, isoleucine, 3-aminobutyric acid, 4-aminocyclohexanecarboxylic acid, phenylalanine, methionine, aminobenzoic acid, aspartic acid, glutamic acid, lysine, lanthionine, 1-amino-2·3·4-butanetricarboxylic acid, lactams of the above amino acids, pyrrolidone, caprolactam, laurolactam, etc.

[0290] The compound containing the alcoholic hydroxy group is preferably an amino alcohol inorganic acid salt.

[0291] The amino alcohol inorganic acid salt can be produced by reacting the amino acid inorganic acid salt with an alcohol.

[0292] The amino alcohol inorganic acid salt is an inorganic acid salt of an amino alcohol having 1 primary or secondary hydroxy group and 1 primary amino group and having 2 to 12 carbon atoms. The above amino alcohol may contain a hetero atom such as oxygen or sulfur in its alkylene chain, or a substituent group such as a nitro, halogen, alkyl, phenyl group, etc. which is inert to an esterification reaction.

[0293] Specific examples of the amino alcohol include ethanolamine, 1-amino-2-propanol, 2-amino-1-propanol, 2-aminoisobutanol, 2-amino-1-butanol, 2-(2-aminoethoxy)-ethanol, 2-aminocyclohexanol, etc.

[0294] Known alcohols can be used, but preferably, they are monoalcohols having 1 to 10 carbon atoms. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, octanol, decanol, cyclopentanol, cyclohexanol, etc. may be mentioned. When these compounds contain isomers, the isomers can also be used.

[0295] [Hydroxy compound] Examples of the hydroxy compound include alcohols and aromatic hydroxy compounds.

[0296] Examples of the alcohols include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3 - butanediol, 1,4 - butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, ethanolamine, propanolamine (1 - amino - 2 - propanol), dimethanolamine, diethanolamine, dipropanolamine, 1 - amino - 2 - butanol, etc.

[0297] Specific examples of the aromatic hydroxy compounds include, for example, compounds represented by the general formula (VI) (hereinafter, may be referred to as "aromatic hydroxy compound (VI)") and the like.

[0298] [Chemical formula]

[0299] (In general formula (VI), ring A 61 is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. R 61 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or a hydroxy group. R 61 may combine with ring A 61 to form a ring structure. Further, n61 is an integer of 1 or more and 10 or less.)

[0300] [R 61 R 61 Examples of the alkyl group having 1 to 20 carbon atoms in R include a methyl group, an ethyl group, a propyl group (each isomer), a butyl group (each isomer), a pentyl group (each isomer), a hexyl group (each isomer), a heptyl group (each isomer), an octyl group (each isomer), a nonyl group (each isomer), a decyl group (each isomer), a dodecyl group (each isomer), an octadecyl group (each isomer), and the like.

[0301] R 61 Examples of the alkoxy group having 1 to 20 carbon atoms in R include a methoxy group, an ethoxy group, a propoxy group (each isomer), a butyloxy group (each isomer), a pentyloxy group (each isomer), a hexyloxy group (each isomer), a heptyloxy group (each isomer), an octyloxy group (each isomer), a nonyloxy group (each isomer), a decyloxy group (each isomer), a dodecyloxy group (each isomer), an octadecyloxy group (each isomer), and the like.

[0302] R 61 Examples of the aryl group having 6 to 20 carbon atoms in R include a phenyl group, a naphthyl group, and the like.

[0303] R 61 ​Examples of the aryl group having an alkyl group as a substituent include methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), biphenyl group (each isomer), dimethylphenyl group (each isomer), diethylphenyl group (each isomer), dipropylphenyl group (each isomer), dibutylphenyl group (each isomer), dipentylphenyl group (each isomer), dihexylphenyl group (each isomer), diheptylphenyl group (each isomer), terphenyl group (each isomer), trimethylphenyl group (each isomer), triethylphenyl group (each isomer), tripropylphenyl group (each isomer), tributylphenyl group (each isomer), etc.

[0304] R 61 Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group, methylphenoxy group (each isomer), ethylphenoxy group (each isomer), propylphenoxy group (each isomer), butylphenoxy group (each isomer), pentylphenoxy group (each isomer), hexylphenoxy group (each isomer), heptylphenoxy group (each isomer), octylphenoxy group (each isomer), nonylphenoxy group (each isomer), decylphenoxy group (each isomer), phenylphenoxy group (each isomer), dimethylphenoxy group (each isomer), diethylphenoxy group (each isomer), dipropylphenoxy group (each isomer), dibutylphenoxy group (each isomer), dipentylphenoxy group (each isomer), dihexylphenoxy group (each isomer), diheptylphenoxy group (each isomer), diphenylphenoxy group (each isomer), trimethylphenoxy group (each isomer), triethylphenoxy group (each isomer), tripropylphenoxy group (each isomer), tributylphenoxy group (each isomer), etc.

[0305] R 61Examples of the aralkyl group having 7 to 20 carbon atoms include phenylmethyl group, phenylethyl group (each isomer), phenylpropyl group (each isomer), phenylbutyl group (each isomer), phenylpentyl group (each isomer), phenylhexyl group (each isomer), phenylheptyl group (each isomer), phenyloctyl group (each isomer), phenylnonyl group (each isomer), and the like.

[0306] R 61 Examples of the aralkyloxy group having 7 to 20 carbon atoms include phenylmethoxy group, phenylethoxy group (each isomer), phenylpropyloxy group (each isomer), phenylbutyloxy group (each isomer), phenylpentyloxy group (each isomer), phenylhexyloxy group (each isomer), phenylheptyloxy group (each isomer), phenyloctyloxy group (each isomer), phenylnonyloxy group (each isomer), and the like.

[0307] [A 61 Ring A 61 is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. Ring A 61 may be a monocyclic ring, a polycyclic ring, or a condensed ring. Ring A 61 Specific examples of Ring A include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentalene ring, azulene ring, heptalene ring, indacene ring, biphenylene ring, acenaphthylene ring, aceanthrylene ring, acephenanthrylene ring, and the like. Among them, as Ring A 11 benzene ring, naphthalene ring, or anthracene ring is preferable, and benzene ring is more preferable.

[0308] In addition, these rings may have substituents other than the above R 61 . Substituents other than R 61 include the same ones as those exemplified in R 61 . R 61 and R 61 ​The other substituents consist of different functional groups.

[0309] [n61] n61 represents the number of the substituent R 61 and is an integer of 1 or more and 10 or less.

[0310] In the general formula (VI), as the compound in which ring A 61 is a benzene ring, for example, compounds represented by the following general formula (VI-1) etc. can be mentioned.

[0311] [Chemical formula]

[0312] (In the general formula (VI-1), R 611 ~R 615 are each independently the same as the above R 61 .)

[0313] Among them, it is preferable that at least one of R 611 ~R 615 is a hydrogen atom, and it is more preferable that all of R 611 ~R 615 are hydrogen atoms.

[0314] Preferred hydroxy compounds include, for example, phenol, 2-ethylphenol, 2-propylphenol (each isomer), 2-butylphenol (each isomer), 2-pentylphenol (each isomer), 2-hexylphenol (each isomer), 2-heptylphenol (each isomer), 2-phenylphenol, 2,6-dimethylphenol, 2,4-diethylphenol, 2,6-diethylphenol, 2,4-dipropylphenol (each isomer), 2,6-dipropylphenol (each isomer), 2,4-dibutylphenol (each isomer), 2,4-dipentylphenol (each isomer), 2,4-dihexylphenol (each isomer), 2,4-diheptylphenol (each isomer), 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol (each isomer), 2-methyl-6-butylphenol (each isomer), 2-methyl-6-pentylphenol (each isomer), 2-ethyl-6-propylphenol (each isomer), 2-ethyl-6-butylphenol (each isomer), 2-ethyl-6-pentylphenol (each isomer), 2-propyl-6-butylphenol (each isomer), 2-ethyl-4-methylphenol (each isomer), 2-ethyl-4-propylphenol (each isomer), 2-ethyl-4-butylphenol (each isomer), 2-ethyl-4-pentylphenol (each isomer), 2-ethyl-4-hexylphenol (each isomer), 2-ethyl-4-heptylphenol (each isomer), 2-ethyl-4-octylphenol (each isomer), 2-ethyl-4-phenylphenol (each isomer), 2-ethyl-4-cumylphenol (each isomer), 2-propyl-4-methylphenol (each isomer), 2-propyl-4-ethylphenol (each isomer), 2-propyl-4-butylphenol (each isomer), 2-propyl-4-pentylphenol (each isomer), 2-propyl-4-hexylphenol (each isomer), 2-propyl-4-heptylphenol (each isomer), 2-propyl-4-octylphenol (each isomer), 2-propyl-4-phenylphenol (each isomer), 2-propyl-4-cumylphenol (each isomer), 2-butyl-4-methylphenol (each isomer), 2-butyl-4-ethylphenol (each isomer), 2-butyl-4-propylphenol (each isomer),2-Butyl-4-pentylphenol (each isomer), 2-butyl-4-hexylphenol (each isomer), 2-butyl-4-heptylphenol (each isomer), 2-butyl-4-octylphenol (each isomer), 2-butyl-4-phenylphenol (each isomer), 2-butyl-4-cumylphenol (each isomer), 2-pentyl-4-methylphenol (each isomer), 2-pentyl-4-ethylphenol (each isomer), 2-pentyl-4-propylphenol (each isomer), 2-pentyl-4-butylphenol (each isomer), 2-pentyl-4-hexylphenol (each isomer), 2-pentyl-4-heptylphenol (each isomer), 2-pentyl-4-octylphenol (each isomer), 2-pentyl-4-phenylphenol (each isomer), 2-pentyl-4-cumylphenol (each isomer), 2-hexyl-4-methylphenol (each isomer), 2-hexyl-4-ethylphenol (each isomer), 2-hexyl-4-propylphenol (each isomer), 2-hexyl-4-butylphenol (each isomer), 2-hexyl-4-pentylphenol (each isomer), 2-hexyl-4-heptylphenol (each isomer), 2-hexyl-4-octylphenol (each isomer), 2-hexyl-4-phenylphenol (each isomer), 2-hexyl-4-cumylphenol (each isomer), 2-heptyl-4-methylphenol (each isomer), 2-heptyl-4-ethylphenol (each isomer), 2-heptyl-4-propylphenol (each isomer), 2-heptyl-4-butylphenol (each isomer), 2-heptyl-4-pentylphenol (each isomer), 2-heptyl-4-hexylphenol (each isomer), 2-heptyl-4-octylphenol (each isomer), 2-heptyl-4-phenylphenol (each isomer), 2-heptyl-4-cumylphenol (each isomer), 2,4,6-trimethylphenol, 2,6-dimethyl-4-ethylphenol, 2,6-dimethyl-4-propylphenol (each isomer), 2,6-dimethyl-4-butylphenol (each isomer), 2,6-dimethyl-4-pentylphenol (each isomer), 2,6-dimethyl-4-hexylphenol (each isomer), 2,6-dimethyl-4-phenylphenol, 2,6-dimethyl-4-cumylphenol,2,4,6-Triethylphenol, 2,6-Diethyl-4-methylphenol, 2,6-Diethyl-4-propylphenol (each isomer), 2,6-Diethyl-4-butylphenol (each isomer), 2,6-Diethyl-4-pentylphenol (each isomer), 2,6-Diethyl-4-hexylphenol (each isomer), 2,6-Diethyl-4-phenylphenol, 2,6-Diethyl-4-cumylphenol, 2,4,6-Tripropylphenol (each isomer), 2,6-Dipropyl-4-ethylphenol (each isomer), 2,6-Dipropyl-4-methylphenol (each isomer), 2,6-Dipropyl-4-butylphenol (each isomer), 2,6-Dipropyl-4-pentylphenol (each isomer), 2,6-Dipropyl-4-hexylphenol (each isomer), 2,6-Dipropyl-4-phenylphenol (each isomer), 2,6-Dipropyl-4-cumylphenol (each isomer), 2,4-Dimethyl-6-ethylphenol, 2-Methyl-4,6-diethylphenol, 2-Methyl-4-propyl-6-ethylphenol (each isomer), 2-Methyl-4-butyl-6-ethylphenol (each isomer), 2-Methyl-4-pentyl-6-ethylphenol (each isomer), 2-Methyl-4-hexyl-6-ethylphenol (each isomer), 2-Methyl-4-phenyl-6-ethylphenol (each isomer), 2-Methyl-4-cumyl-6-ethylphenol (each isomer), 2,4-Dimethyl-6-propylphenol (each isomer), 2-Methyl-4,6-dipropylphenol (each isomer), 2-Methyl-4-ethyl-6-propylphenol (each isomer), 2-Methyl-4-butyl-6-propylphenol (each isomer), 2-Methyl-4-pentyl-6-propylphenol (each isomer), 2-Methyl-4-hexyl-6-propylphenol (each isomer), 2-Methyl-4-phenyl-6-propylphenol (each isomer), 2-Methyl-4-cumyl-6-propylphenol (each isomer), 2,4-Dimethyl-6-butylphenol, 2-Methyl-4,6-dibutylphenol, 2-Methyl-4-propyl-6-butylphenol (each isomer), 2-Methyl-4-ethyl-6-butylphenol (each isomer), 2-Methyl-4-pentyl-6-butylphenol (each isomer),2-Methyl-4-hexyl-6-butylphenol (each isomer), 2-methyl-4-phenyl-6-butylphenol (each isomer), 2-methyl-4-cumyl-6-butylphenol (each isomer), 2,4-dimethyl-6-pentylphenol, 2-methyl-4,6-dipentylphenol, 2-methyl-4-propyl-6-pentylphenol (each isomer), 2-methyl-4-butyl-6-pentylphenol (each isomer), 2-methyl-4-ethyl-6-pentylphenol (each isomer), 2-methyl-4-hexyl-6-pentylphenol (each isomer), 2-methyl-4-phenyl-6-pentylphenol (each isomer), 2-methyl-4-cumyl-6-pentylphenol (each isomer), 2,4-dimethyl-6-hexylphenol, 2-methyl-4,6-dihexylphenol, 2-methyl-4-propyl-6-hexylphenol (each isomer), 2-methyl-4-butyl-6-hexylphenol (each isomer), 2-methyl-4-pentyl-6-hexylphenol (each isomer), 2-methyl-4-ethyl-6-hexylphenol (each isomer), 2-methyl-4-phenyl-6-hexylphenol (each isomer), 2-methyl-4-cumyl-6-hexylphenol (each isomer), 2-ethyl-4-methyl-6-propylphenol (each isomer), 2,4-diethyl-6-propylphenol (each isomer), 2-ethyl-4,6-propylphenol (each isomer), 2-ethyl-4-butyl-6-propylphenol (each isomer), 2-ethyl-4-pentyl-6-propylphenol (each isomer), 2-ethyl-4-hexyl-6-propylphenol (each isomer), 2-ethyl-4-heptyl-6-propylphenol (each isomer), 2-ethyl-4-octyl-6-propylphenol (each isomer), 2-ethyl-4-phenyl-6-propylphenol (each isomer), 2-ethyl-4-cumyl-6-propylphenol (each isomer), 2-ethyl-4-methyl-6-butylphenol (each isomer), 2,4-diethyl-6-butylphenol (each isomer), 2-ethyl-4,6-butylphenol (each isomer), 2-ethyl-4-propyl-6-butylphenol (each isomer), 2-ethyl-4-pentyl-6-butylphenol (each isomer),2-Ethyl-4-hexyl-6-butylphenol (each isomer), 2-ethyl-4-heptyl-6-butylphenol (each isomer), 2-ethyl-4-octyl-6-butylphenol (each isomer), 2-ethyl-4-phenyl-6-butylphenol (each isomer), 2-ethyl-4-cumyl-6-butylphenol (each isomer), 2-ethyl-4-methyl-6-pentylphenol (each isomer), 2,4-diethyl-6-pentylphenol (each isomer), 2-ethyl-4,6-pentylphenol (each isomer), 2-ethyl-4-butyl-6-pentylphenol (each isomer), 2-ethyl-4-propyl-6-pentylphenol (each isomer), 2-ethyl-4-hexyl-6-pentylphenol (each isomer), 2-ethyl-4-heptyl-6-pentylphenol (each isomer), 2-ethyl-4-octyl-6-pentylphenol (each isomer), 2-ethyl-4-phenyl-6-pentylphenol (each isomer), 2-ethyl-4-cumyl-6-pentylphenol (each isomer), 2-ethyl-4-methyl-6-hexylphenol (each isomer), 2,4-diethyl-6-hexylphenol (each isomer), 2-ethyl-4,6-hexylphenol (each isomer), 2-ethyl-4-propyl-6-hexylphenol (each isomer), 2-ethyl-4-pentyl-6-hexylphenol (each isomer), 2-ethyl-4-butyl-6-hexylphenol (each isomer), 2-ethyl-4-heptyl-6-hexylphenol (each isomer), 2-ethyl-4-octyl-6-hexylphenol (each isomer), 2-ethyl-4-phenyl-6-hexylphenol (each isomer), 2-ethyl-4-cumyl-6-hexylphenol (each isomer), 2-propyl-4-methyl-6-butylphenol (each isomer), 2,4-dipropyl-6-butylphenol (each isomer), 2-propyl-4,6-butylphenol (each isomer), 2-propyl-4-ethyl-6-butylphenol (each isomer), 2-propyl-4-pentyl-6-butylphenol (each isomer), 2-propyl-4-hexyl-6-butylphenol (each isomer), 2-propyl-4-heptyl-6-butylphenol (each isomer), 2-propyl-4-octyl-6-butylphenol (each isomer),2-Propyl-4-phenyl-6-butylphenol (each isomer), 2-propyl-4-cumyl-6-butylphenol (each isomer), 2,4-dicumylphenol, methoxyphenol (each isomer), ethoxyphenol (each isomer), etc. are mentioned. Among these, phenol, methoxyphenol (each isomer), or ethoxyphenol (each isomer) is preferable.

[0315] As the hydroxy compound, it is preferable that it is a hydroxy compound having a standard boiling point lower than the standard boiling point of the isocyanate compound generated from the above-mentioned N-substituted carbamate compound.

[0316] [Carbonic acid derivative] Examples of the carbonic acid derivative include urea, urea derivatives, carbonic esters, etc. Details of the carbonic esters will be described later.

[0317] Examples of the urea derivative include a compound represented by the general formula (IV) (hereinafter, may be referred to as "urea derivative (IV)") obtained by the following reaction formula.

[0318] [Chemical formula]

[0319] In the general formula (IV), R 41 is a hydrogen atom or a monovalent organic group.

[0320] (R 41 ) R 41 Examples of the monovalent organic group in are the same as those of R 52 described later. Among them, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferable, and an alkyl group having 1 to 10 carbon atoms is more preferable.

[0321] In the above reaction formula, for the sake of simplicity of explanation, a case is shown where a primary amine having one primary amino group in one molecule (that is, a monofunctional primary amine) of one type is used and urea is used as the carbonic acid derivative. However, when the primary amine to be used is a primary amine having two or more primary amino groups in one molecule (that is, a polyfunctional primary amine of bifunctional or higher), or when a compound other than urea, for example, N-alkyl urea or N,N'-dialkyl urea in which each amino group of urea is substituted with an alkyl group, is used as the carbonic acid derivative, it can be easily understood by those skilled in the art that the same reaction occurs.

[0322] As the urea derivative (IV) obtained in the above reaction formula, when N-alkyl urea is used in step (1), the by-produced low-boiling compounds are ammonia and the alkylamine corresponding to the alkyl group. When N,N'-dialkyl urea is used in step (1), the by-produced low-boiling compound is the alkylamine corresponding to the alkyl group.

[0323] [N-Substituted Carbamate Compound] Examples of the N-substituted carbamate compound include a compound represented by the general formula (V) (hereinafter, may be referred to as "carbamate compound (V)") and the like.

[0324] [Chemical Formula]

[0325] (In the general formula (V), R 51 is a divalent or higher organic group, and R 52 is a monovalent organic group. n51 is an integer of 2 or more.)

[0326] (R 51 ) In the general formula (V), R 51 is a divalent or higher organic group, and is preferably a divalent or higher and decavalent or lower organic group. Among them, R 51It is preferably an aliphatic hydrocarbon group having 1 to 4 ester groups or nitrogen atoms and having 2 to 4 valences and 1 to 20 carbon atoms, or an aromatic group having 1 to 4 ester groups or nitrogen atoms and having 2 to 3 valences and 6 to 20 carbon atoms.

[0327] R 51 Examples of the aliphatic hydrocarbon group in R include an alkylene group, an alkanetriyl group, a cycloalkyl group, a cycloalkylene group, a cycloalkanetriyl group, or a group composed of the alkyl group, the alkylene group, or the alkanetriyl group and the cycloalkyl group, the cycloalkylene group, or the cycloalkanetriyl group. A linear or branched alkylene group, an alkanetriyl group, a cycloalkylene group, a cycloalkanetriyl group, or a group composed of the alkylene group or the alkanetriyl group and the cycloalkyl group, the cycloalkylene group, or the cycloalkanetriyl group is more preferable.

[0328] Examples of the linear or branched alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, a pentylene group, an n-hexylene group, a decamethylene group, and the like.

[0329] Examples of the cycloalkylene group include a cyclobutylene group, a cyclohexylene group, and the like.

[0330] Examples of the linear or branched alkanetriyl group include a hexanetriyl group, a nonanetriyl group, a decanetriyl group, and the like.

[0331] Examples of the cycloalkanetriyl group include a cyclopropanetriyl group, a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, and the like.

[0332] R 51As the aromatic hydrocarbon group in , a group having a substituted or unsubstituted aromatic ring with 6 to 13 carbon atoms is preferable. Examples of the substituent include an alkyl group, an aryl group, an aralkyl group, etc. The aromatic ring may be an aromatic hydrocarbon ring or a heteroaromatic ring. Specifically, for example, a benzene ring, a naphthalene ring, a pyridine ring, etc. may be mentioned.

[0333] R 51 When the aliphatic hydrocarbon group or aromatic group in has 1 to 4 ester groups, R 51 is preferably a group excluding the primary amino group at the end of an amine compound having an ester group obtained by reacting the carboxy group of an amino acid with a hydroxy compound.

[0334] Specific examples of the amine compound having an ester group include, for example, 2-aminoethyl acrylate, 2-aminoethyl 2-methylacrylate, 2-aminopropyl acrylate, 2-aminopropyl 2-methylacrylate, 3-aminopropyl acrylate, 3-aminopropyl 2-methylacrylate, 4-aminobutyl acrylate, 4-aminobutyl 2-methylacrylate, 5-aminopentyl acrylate, 5-aminopentyl 2-methylacrylate, 6-aminohexyl acrylate, 6-aminohexyl 2-methylacrylate, 8-aminooctyl acrylate, 8-aminooctyl 2-methylacrylate, 10-aminodecyl acrylate, 10-aminodecyl 2-methylacrylate, 11-aminoundecyl acrylate, 11-aminoundecyl 2-methylacrylate, 12-aminododecyl acrylate, 12-aminododecyl 2-methylacrylate, lysine methyl ester diamine, lysine ethyl ester diamine, 2-aminoethyl 2,5-diaminopentanoate, 2-aminoethyl 2,6-diaminohexanoate, bis(2-aminoethyl) 2-aminobutanedioate, bis(2-aminoethyl) 2-aminopentanedioate, tris(2-aminoethyl) hexane-1,3,6-tricarboxylate, and the like.

[0335] Examples of the amino acid used for producing the amine compound having an ester group include lysine, alanine, arginine, asparagine, glutamine, glycine, aspartic acid, glutamic acid, ornithine, histidine, isoleucine, leucine, methionine, phenylalanine, tryptophan, and valine. Among them, as the amino acid, lysine, arginine, glycine, aspartic acid, glutamic acid, or ornithine is preferable, and lysine, arginine, glycine, aspartic acid, or glutamic acid is more preferable.

[0336] Examples of the hydroxy compound used for producing the amine compound having an ester group include alcohols and aromatic hydroxy compounds.

[0337] Examples of the alcohols include methyl alcohol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dotecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3 - butanediol, 1,4 - butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol, ethanolamine, propanolamine (1 - amino - 2 - propanol), dimethanolamine, diethanolamine, dipropanolamine, 1 - amino - 2 - butanol, and the like.

[0338] Examples of the aromatic hydroxy compounds include monophenols such as phenol (carbolic acid), 2 - methoxyphenol, cresol, xylenol, carvacrol, thymol, naphthol, and polyhydric phenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin.

[0339] R 51 When the aliphatic hydrocarbon group or aromatic group in R has 1 to 4 nitrogen atoms, R 51Preferably, it is an organic group obtained by removing the terminal amino group from an amine compound having 1 to 4 secondary or tertiary amines other than the terminals of an aliphatic hydrocarbon group or an aromatic group. Specific examples of the amine compound having 1 to 4 secondary or tertiary amines other than the terminals of an aliphatic hydrocarbon group or an aromatic group include, for example, 2-(dimethylamino)ethylamine, 2-(diethylamino)ethylamine, 2-(diisopropylamino)ethylamine, 2-(cyclohexylamino)ethylamine, 3-(cyclohexylamino)propylamine, 3-(diethylamino)propylamine, 3-(dimethylamino)propylamine, diethylenetriamine, diisopropyltriamine, bis-(3-aminopropyl)methylenamine, 3-(2-aminoethylamino)propylamine, N,N'-bis(3-aminopropyl)ethylenediamine, 1-(3-aminopropyl)imidazole, trisaminoethylamine, trisaminopropylamine, and the like. Among them, as the amine compound, it is preferably an amine compound having 1 to 2 tertiary amines other than the terminals and having an aliphatic hydrocarbon group or an aromatic group, and more preferably an amine compound having 1 tertiary amine other than the terminals and having an aliphatic hydrocarbon group or an aromatic group.

[0340] (R 52 ) In the general formula (V), R 52 is a monovalent organic group. Among them, R 52 is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom.

[0341] R 52Examples of the aliphatic hydrocarbon group include alkyl groups such as methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), hexyl group (each isomer), heptyl group (each isomer), octyl group (each isomer), nonyl group (each isomer), decyl group (each isomer), undecyl group (each isomer), dodecyl group (each isomer), tridecyl group (each isomer), tetradecyl group (each isomer), pentadecyl group (each isomer), hexadecyl group (each isomer), heptadecyl group (each isomer), octadecyl group (each isomer), nonadecyl (each isomer), and eicosyl group (each isomer); cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group, etc.

[0342] R 52Examples of the aliphatic hydrocarbon group which may contain an oxygen atom include a methoxymethyl group, a methoxyethyl group (each isomer), a methoxypropyl group (each isomer), a methoxybutyl group (each isomer), a methoxypentyl group (each isomer), a methoxyhexyl group (each isomer), a methoxyheptyl group (each isomer), a methoxyoctyl group (each isomer), a methoxynonyl group (each isomer), a methoxydecyl group (each isomer), a methoxyundecyl group (each isomer), a methoxydodecyl group (each isomer), a methoxytetradecyl group (each isomer), a methoxypentadecyl group (each isomer), a methoxyhexadecyl group (each isomer), a methoxyheptadecyl group (each isomer), a methoxyoctadecyl group (each isomer), a methoxynonadecyl (each isomer), an ethoxymethyl group, an ethoxyethyl group (each isomer), an ethoxypropyl group (each isomer), an ethoxybutyl group (each isomer), an ethoxypentyl group (each isomer), an ethoxyhexyl group (each isomer), an ethoxyheptyl group (each isomer), an ethoxyoctyl group (each isomer), an ethoxynonyl group (each isomer), an ethoxydecyl group (each isomer), an ethoxyundecyl group (each isomer), an ethoxydodecyl group (each isomer), an ethoxytetradecyl group (each isomer), an ethoxypentadecyl group (each isomer), an ethoxyhexadecyl group (each isomer), an ethoxyheptadecyl group (each isomer), an ethoxyoctadecyl group (each isomer), a propyloxymethyl group (each isomer), a propyloxyethyl group (each isomer), a propyloxypropyl group (each isomer), a propyloxybutyl group (each isomer), a propyloxypentyl group (each isomer), a propyloxyhexyl group (each isomer), a propyloxyheptyl group (each isomer), a propyloxyoctyl group (each isomer), a propyloxynonyl group (each isomer), a propyloxydecyl group (each isomer), a propyloxyundecyl group (each isomer), a propyloxydodecyl group (each isomer), a propyloxytetradecyl group (each isomer), a propyloxypentadecyl group (each isomer), a propyloxyhexadecyl group (each isomer), a propyloxyheptadecyl group (each isomer), a butyloxymethyl group (each isomer), a butyloxyethyl group (each isomer),Butyloxypropyl group (each isomer), butyloxybutyl group (each isomer), butyloxypentyl group (each isomer), butyloxyhexyl group (each isomer), butyloxyheptyl group (each isomer), butyloxyoctyl group (each isomer), butyloxynonyl group (each isomer), butyloxydecyl group (each isomer), butyloxyundecyl group (each isomer), butyloxydodecyl group (each isomer), butyloxytetradecyl group (each isomer), butyloxypentadecyl group (each isomer), butyloxyhexadecyl group (each isomer), pentyloxymethyl group (each isomer), pentyloxyethyl group (each isomer), pentyloxypropyl group (each isomer), pentyloxybutyl group (each isomer), pentyloxypentyl group (each isomer), pentyloxyhexyl group (each isomer), pentyloxyheptyl group (each isomer), pentyloxyoctyl group (each isomer), pentyloxynonyl group (each isomer), pentyloxydecyl group (each isomer), pentyloxyundecyl group (each isomer), pentyloxydodecyl group (each isomer), pentyloxytetradecyl group (each isomer), pentyloxypentadecyl group (each isomer), hexyloxymethyl group (each isomer), hexyloxyethyl group (each isomer), hexyloxypropyl group (each isomer), hexyloxybutyl group (each isomer), hexyloxypentyl group (each isomer), hexyloxyhexyl group (each isomer), hexyloxyheptyl group (each isomer), hexyloxyoctyl group (each isomer), hexyloxynonyl group (each isomer), hexyloxydecyl group (each isomer), hexyloxyundecyl group (each isomer), hexyloxydodecyl group (each isomer), hexyloxytetradecyl group (each isomer), heptyloxymethyl group (each isomer), heptyloxyethyl group (each isomer), heptyloxypropyl group (each isomer), heptyloxybutyl group (each isomer), heptyloxypentyl group (each isomer), heptyloxyhexyl group (each isomer), heptyloxyheptyl group (each isomer), heptyloxyoctyl group (each isomer), heptyloxynonyl group (each isomer), heptyloxydecyl group (each isomer),Heptyloxyundecyl group (each isomer), heptyloxydodecyl group (each isomer), heptyloxytetradecyl group (each isomer), octyloxymethyl group (each isomer), octyloxyethyl group (each isomer), octyloxypropyl group (each isomer), octyloxybutyl group (each isomer), octyloxypentyl group (each isomer), octyloxyhexyl group (each isomer), octyloxyheptyl group (each isomer), octyloxyoctyl group (each isomer), octyloxynonyl group (each isomer), octyloxydodecyl group (each isomer), octyloxyundecyl group (each isomer), octyloxydodecyl group (each isomer), nonyloxymethyl group (each isomer), nonyloxyethyl group (each isomer), nonyloxypropyl group (each isomer), nonyloxybutyl group (each isomer), nonyloxypentyl group (each isomer), nonyloxyhexyl group (each isomer), nonyloxyheptyl group (each isomer), nonyloxyoctyl group (each isomer), nonyloxynonyl group (each isomer), nonyloxydodecyl group (each isomer), nonyloxyundecyl group (each isomer), decyloxymethyl group (each isomer), decyloxyethyl group (each isomer), decyloxypropyl group (each isomer), decyloxybutyl group (each isomer), decyloxypentyl group (each isomer), decyloxyhexyl group (each isomer), decyloxyheptyl group (each isomer), decyloxyoctyl group (each isomer), decyloxynonyl group (each isomer), decyloxydodecyl group (each isomer), undecyloxymethyl group (each isomer), undecyloxyethyl group (each isomer), undecyloxypropyl group (each isomer), undecyloxybutyl group (each isomer), undecyloxypentyl group (each isomer), undecyloxyhexyl group (each isomer), undecyloxyheptyl group (each isomer), undecyloxyoctyl group (each isomer), undecyloxynonyl group (each isomer), dodecyloxymethyl group (each isomer), dodecyloxyethyl group (each isomer), dodecyloxypropyl group (each isomer), dodecyloxybutyl group (each isomer), dodecyloxypentyl group (each isomer), dodecyloxyhexyl group (each isomer), dodecyloxyheptyl group (each isomer), dodecyldecyloxyoctyl group (each isomer), tridecyloxymethyl group (each isomer),Tridecyloxyethyl groups (each isomer), tridecyloxypropyl groups (each isomer), tridecyloxybutyl groups (each isomer), tridecyloxypentyl groups (each isomer), tridecyloxyhexyl groups (each isomer), tridecyloxyheptyl groups (each isomer), tetradecyloxymethyl groups (each isomer), tetradecyloxyethyl groups (each isomer), tetradecyloxypropyl groups (each isomer), tetradecyloxybutyl groups (each isomer), tetradecyloxypentyl groups (each isomer), tetradecyloxyhexyl groups (each isomer), pentadecyloxymethyl groups, pentadecyloxyethyl groups (each isomer), pentadecyloxypropyl groups (each isomer), pentadecyloxybutyl groups (each isomer), pentadecyloxypentyl groups (each isomer), hexadecyloxymethyl groups (each isomer), hexadecyloxyethyl groups (each isomer), hexadecyloxypropyl groups (each isomer), hexadecyloxybutyl groups (each isomer), heptadecyloxymethyl groups (each isomer), heptadecyloxyethyl groups (each isomer), heptadecyloxypropyl groups (each isomer), octadecyloxymethyl groups (each isomer), octadecyloxyethyl groups (each isomer), and other alkoxyalkyl groups such as these can be mentioned.

[0343] R 52Examples of the aromatic hydrocarbon group include aryl groups such as phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group; methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer), propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer),Aryl groups having an alkyl group such as a butylnonylphenyl group (each isomer), a butyldecylphenyl group (each isomer), a dipentylphenyl group (each isomer), a pentylhexylphenyl group (each isomer), a pentylheptylphenyl group (each isomer), a pentyloctylphenyl group (each isomer), a pentylnonylphenyl group (each isomer), a dihexylphenyl group (each isomer), a hexylheptylphenyl group (each isomer), a hexyloctylphenyl group (each isomer), a diheptylphenyl group (each isomer), a trimethylphenyl group (each isomer), a dimethylethylphenyl group (each isomer), a dimethylpropylphenyl group (each isomer), a dimethylbutylphenyl group (each isomer), a dimethylpentylphenyl group (each isomer), a dimethylhexylphenyl group (each isomer), a dimethylheptylphenyl group (each isomer), a dimethyloctylphenyl group (each isomer), a dimethylnonylphenyl group (each isomer), a dimethyldecylphenyl group (each isomer), a dimethylundecylphenyl group (each isomer), a dimethyldodecylphenyl group (each isomer), a triethylphenyl group (each isomer), a diethylmethylphenyl group (each isomer), a diethylpropylphenyl group (each isomer), a diethylbutylphenyl group (each isomer), a diethylpentylphenyl group (each isomer), a diethylhexylphenyl group (each isomer), a diethylheptylphenyl group (each isomer), a diethyloctylphenyl group (each isomer), a diethylnonylphenyl group (each isomer), a diethyldecylphenyl group (each isomer), a tripropylphenyl group (each isomer), a dipropylmethylphenyl group (each isomer), a dipropylethylphenyl group (each isomer), a dipropylbutylphenyl group (each isomer), a dipropylpentylphenyl group (each isomer), a dipropylhexylphenyl group (each isomer), a dipropylheptylphenyl group (each isomer), a dipropyloctylphenyl group (each isomer), a tributylphenyl group (each isomer), a dibutylmethylphenyl group (each isomer), a dibutylethylphenyl group (each isomer), a dibutylpropylphenyl group (each isomer), a dibutylpentylphenyl group (each isomer), a dibutylhexylphenyl group (each isomer) as a substituent, etc. are mentioned.

[0344] R 52Examples of the aromatic hydrocarbon group which may contain an oxygen atom include alkoxyaryl groups such as a methoxyphenyl group (each isomer), an ethoxyphenyl group (each isomer), and the like.

[0345] Among them, R 52Examples include a phenyl group, a naphthyl group, an anthryl group, a pyrenyl group, a phenanthryl group, a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer), a pentylphenyl group (each isomer), a hexylphenyl group (each isomer), a heptylphenyl group (each isomer), an octylphenyl group (each isomer), a nonylphenyl group (each isomer), a decylphenyl group (each isomer), an undecylphenyl group (each isomer), a dodecylphenyl group (each isomer), a tridecylphenyl group (each isomer), a tetradecylphenyl group (each isomer), a dimethylphenyl group (each isomer), a methylethylphenyl group (each isomer), a methylpropylphenyl group (each isomer), a methylbutylphenyl group (each isomer), a methylpentylphenyl group (each isomer), a methylhexylphenyl group (each isomer), a methylheptylphenyl group (each isomer), a methyloctylphenyl group (each isomer), a methylnonylphenyl group (each isomer), a methyldecylphenyl group (each isomer), a methylundecylphenyl group (each isomer), a methyldodecylphenyl group (each isomer), a methyldodecylphenyl group (each isomer), a methyltridecylphenyl group (each isomer), a diethylphenyl group (each isomer), an ethylpropylphenyl group (each isomer), an ethylbutylphenyl group (each isomer), an ethylpentylphenyl group (each isomer), an ethylhexylphenyl group (each isomer), an ethylheptylphenyl group (each isomer), an ethyloctylphenyl group (each isomer), an ethylnonylphenyl group (each isomer), an ethyldecylphenyl group (each isomer), an ethylundecylphenyl group (each isomer), an ethyldodecylphenyl group (each isomer), a dipropylphenyl group (each isomer), a propylbutylphenyl group (each isomer), a propylpentylphenyl group (each isomer), a propylhexylphenyl group (each isomer), a propylheptylphenyl group (each isomer), a propyloctylphenyl group (each isomer), a propylnonylphenyl group (each isomer), a propyldecylphenyl group (each isomer), a propylundecylphenyl group (each isomer), a dibutylphenyl group (each isomer), a butylpentylphenyl group (each isomer), a butylhexylphenyl group (each isomer), a butylheptylphenyl group (each isomer), a butyloctylphenyl group (each isomer), a butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) is preferable. Further, a phenyl group, a methoxyphenyl group (each isomer), or an ethoxyphenyl group (each isomer) is more preferable.,

[0346] (n51) In general formula (V), n51 represents the number of carbamate groups, is an integer of 2 or more, preferably an integer of 2 or more and 10 or less, more preferably an integer of 3 or more, and even more preferably 3.

[0347] Preferred N-substituted carbamate compounds (V) include, for example, compounds represented by the following formulas (V-1) to (V-5).

[0348] [Chemical formula]

[0349] [Aprotic solvent] As the aprotic solvent, from the viewpoint of not reacting with isocyanate, a carbonic acid derivative, an ether, a hydrocarbon, a ketone, or a mixture thereof is preferable, a carbonic acid derivative, a hydrocarbon, a ketone, or a mixture thereof is more preferable, and a carbonic acid derivative is even more preferable.

[0350] (Carbonic acid derivative) In the present specification, the carbonic acid derivative refers to a compound having a carbonyl group.

[0351] As the carbonic acid derivative, a compound represented by the following general formula (III) (hereinafter, may be referred to as "carbonic acid derivative (III)") is preferable.

[0352] [Chemical formula]

[0353] (In general formula (III), R 31 and R 32 are each independently a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms or an aryloxy group having 6 to 20 carbon atoms.)

[0354] (R 31 and R 32 ) R 31 and R 32 may be the same as or different from each other, but are preferably the same.

[0355] R 31 and R 32 Examples of the alkoxy group having 1 to 20 carbon atoms in R and R include a methoxy group, an ethoxy group, a propyloxy group (each isomer), a butoxy group (each isomer), a hexyloxy group (each isomer), and the like.

[0356] R 31 and R 32 Examples of the aryloxy group having 6 to 20 carbon atoms in R and R include a phenoxy group, a naphthyloxy group, and the like.

[0357] Examples of the substituents of the alkoxy group, aryloxy group, and aralkyloxy group include an alkyl group, an alkoxy group, and the like.

[0358] Among them, R 31 and R 32 are preferably each independently a substituted or unsubstituted aryloxy group having 6 to 20 carbon atoms.

[0359] Preferred carbonic acid derivatives (III) include, for example, carbonic esters and the like.

[0360] A carbonic ester refers to a compound in which one or two atoms of hydrogen of the two atoms of hydrogen of carbonic acid CO(OH)2 are substituted with an alkyl group or an aryl group. The carbonic ester is a compound represented by the following general formula (III-1) (hereinafter, may be referred to as "carbonic ester (III-1)").

[0361]

Chemical formula

[0362] (In the general formula (III-1), R 311 and R312 is each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms.)

[0363] (R 311 and R 312 ) R 311 and R 312 may be the same as or different from each other, but are preferably the same.)

[0364] R 311 and R 312 Examples of the alkyl group having 1 to 20 carbon atoms for R and R include alkyl groups such as methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), hexyl group (each isomer), heptyl group (each isomer), octyl group (each isomer), nonyl group (each isomer), decyl group (each isomer), undecyl group (each isomer), dodecyl group (each isomer), tridecyl group (each isomer), tetradecyl group (each isomer), pentadecyl group (each isomer), hexadecyl group (each isomer), heptadecyl group (each isomer), octadecyl group (each isomer), nonadecyl (each isomer), and eicosyl group (each isomer); cycloalkyl groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and cyclodecyl group, etc.)

[0365] R 311 and R 312 Examples of the aryl group having 6 to 20 carbon atoms for R and R include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, etc.)

[0366] Examples of the substituent of the alkyl group include an alkoxy group, etc.) Examples of the substituent of the aryl group include an alkyl group, an alkoxy group, etc.)

[0367] An alkyl group having an alkoxy group as a substituent, that is, an alkoxyalkyl group includes, for example, a methoxyethyl group (each isomer), a methoxypropyl group (each isomer), a methoxybutyl group (each isomer), a methoxypentyl group (each isomer), a methoxyhexyl group (each isomer), a methoxyheptyl group (each isomer), a methoxyoctyl group (each isomer), a methoxynonyl group (each isomer), a methoxydecyl group (each isomer), a methoxyundecyl group (each isomer), a methoxydodecyl group (each isomer), a methoxytetradecyl group (each isomer), a methoxypentadecyl group (each isomer), a methoxyhexadecyl group (each isomer), a methoxyheptadecyl group (each isomer), a methoxyoctadecyl group (each isomer), a methoxynonadecyl (each isomer), an ethoxymethyl group, an ethoxyethyl group (each isomer), an ethoxypropyl group (each isomer), an ethoxybutyl group (each isomer), an ethoxypentyl group (each isomer), an ethoxyhexyl group (each isomer), an ethoxyheptyl group (each isomer), an ethoxyoctyl group (each isomer), an ethoxynonyl group (each isomer), an ethoxydecyl group (each isomer), an ethoxyundecyl group (each isomer), an ethoxydodecyl group (each isomer), an ethoxytetradecyl group (each isomer), an ethoxypentadecyl group (each isomer), an ethoxyhexadecyl group (each isomer), an ethoxyheptadecyl group (each isomer), an ethoxyoctadecyl group (each isomer), a propyloxymethyl group (each isomer), a propyloxyethyl group (each isomer), a propyloxypropyl group (each isomer), a propyloxybutyl group (each isomer), a propyloxypentyl group (each isomer), a propyloxyhexyl group (each isomer), a propyloxyheptyl group (each isomer), a propyloxyoctyl group (each isomer), a propyloxynonyl group (each isomer), a propyloxydecyl group (each isomer), a propyloxyundecyl group (each isomer), a propyloxydodecyl group (each isomer), a propyloxytetradecyl group (each isomer), a propyloxypentadecyl group (each isomer), a propyloxyhexadecyl group (each isomer), a propyloxyheptadecyl group (each isomer), a butyloxymethyl group (each isomer), a butyloxyethyl group (each isomer),Butyloxypropyl group (each isomer), butyloxybutyl group (each isomer), butyloxypentyl group (each isomer), butyloxyhexyl group (each isomer), butyloxyheptyl group (each isomer), butyloxyoctyl group (each isomer), butyloxynonyl group (each isomer), butyloxydecyl group (each isomer), butyloxyundecyl group (each isomer), butyloxydodecyl group (each isomer), butyloxytetradecyl group (each isomer), butyloxypentadecyl group (each isomer), butyloxyhexadecyl group (each isomer), pentyloxymethyl group (each isomer), pentyloxyethyl group (each isomer), pentyloxypropyl group (each isomer), pentyloxybutyl group (each isomer), pentyloxypentyl group (each isomer), pentyloxyhexyl group (each isomer), pentyloxyheptyl group (each isomer), pentyloxyoctyl group (each isomer), pentyloxynonyl group (each isomer), pentyloxydecyl group (each isomer), pentyloxyundecyl group (each isomer), pentyloxydodecyl group (each isomer), pentyloxytetradecyl group (each isomer), pentyloxypentadecyl group (each isomer), hexyloxymethyl group (each isomer), hexyloxyethyl group (each isomer), hexyloxypropyl group (each isomer), hexyloxybutyl group (each isomer), hexyloxypentyl group (each isomer), hexyloxyhexyl group (each isomer), hexyloxyheptyl group (each isomer), hexyloxyoctyl group (each isomer), hexyloxynonyl group (each isomer), hexyloxydecyl group (each isomer), hexyloxyundecyl group (each isomer), hexyloxydodecyl group (each isomer), hexyloxytetradecyl group (each isomer), heptyloxymethyl group (each isomer), heptyloxyethyl group (each isomer), heptyloxypropyl group (each isomer), heptyloxybutyl group (each isomer), heptyloxypentyl group (each isomer), heptyloxyhexyl group (each isomer), heptyloxyheptyl group (each isomer), heptyloxyoctyl group (each isomer), heptyloxynonyl group (each isomer), heptyloxydecyl group (each isomer),Heptyloxyundecyl group (each isomer), heptyloxydodecyl group (each isomer), heptyloxytetradecyl group (each isomer), octyloxymethyl group (each isomer), octyloxyethyl group (each isomer), octyloxypropyl group (each isomer), octyloxybutyl group (each isomer), octyloxypentyl group (each isomer), octyloxyhexyl group (each isomer), octyloxyheptyl group (each isomer), octyloxyoctyl group (each isomer), octyloxynonyl group (each isomer), octyloxydodecyl group (each isomer), octyloxyundecyl group (each isomer), octyloxydodecyl group (each isomer), nonyloxymethyl group (each isomer), nonyloxyethyl group (each isomer), nonyloxypropyl group (each isomer), nonyloxybutyl group (each isomer), nonyloxypentyl group (each isomer), nonyloxyhexyl group (each isomer), nonyloxyheptyl group (each isomer), nonyloxyoctyl group (each isomer), nonyloxynonyl group (each isomer), nonyloxydodecyl group (each isomer), nonyloxyundecyl group (each isomer), decyloxymethyl group (each isomer), decyloxyethyl group (each isomer), decyloxypropyl group (each isomer), decyloxybutyl group (each isomer), decyloxypentyl group (each isomer), decyloxyhexyl group (each isomer), decyloxyheptyl group (each isomer), decyloxyoctyl group (each isomer), decyloxynonyl group (each isomer), decyloxydodecyl group (each isomer), undecyloxymethyl group (each isomer), undecyloxyethyl group (each isomer), undecyloxypropyl group (each isomer), undecyloxybutyl group (each isomer), undecyloxypentyl group (each isomer), undecyloxyhexyl group (each isomer), undecyloxyheptyl group (each isomer), undecyloxyoctyl group (each isomer), undecyloxynonyl group (each isomer), dodecyloxymethyl group (each isomer), dodecyloxyethyl group (each isomer), dodecyloxypropyl group (each isomer), dodecyloxybutyl group (each isomer), dodecyloxypentyl group (each isomer), dodecyloxyhexyl group (each isomer), dodecyloxyheptyl group (each isomer), dodecyldecyloxyoctyl group (each isomer), tridecyloxymethyl group (each isomer),Tridecyloxyethyl group (each isomer), tridecyloxypropyl group (each isomer), tridecyloxybutyl group (each isomer), tridecyloxypentyl group (each isomer), tridecyloxyhexyl group (each isomer), tridecyloxyheptyl group (each isomer), tetradecyloxymethyl group (each isomer), tetradecyloxyethyl group (each isomer), tetradecyloxypropyl group (each isomer), tetradecyloxybutyl group (each isomer), tetradecyloxypentyl group (each isomer), tetradecyloxyhexyl group (each isomer), pentadecyloxymethyl group, pentadecyloxyethyl group (each isomer), pentadecyloxypropyl group (each isomer), pentadecyloxybutyl group (each isomer), pentadecyloxypentyl group (each isomer), hexadecyloxymethyl group (each isomer), hexadecyloxyethyl group (each isomer), hexadecyloxypropyl group (each isomer), hexadecyloxybutyl group (each isomer), heptadecyloxymethyl group (each isomer), heptadecyloxyethyl group (each isomer), heptadecyloxypropyl group (each isomer), octadecyloxymethyl group (each isomer), octadecyloxyethyl group (each isomer), etc. can be mentioned.

[0368] Examples of aryl groups having an alkyl group as a substituent include methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer), propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer), butyldecylphenyl group (each isomer),Dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), etc. can be mentioned.

[0369] An aryl group having an alkoxy group as a substituent, that is, an alkoxyaryl group includes, for example, a methoxyphenyl group (each isomer), an ethoxyphenyl group (each isomer), and the like.

[0370] Among them, R 311 and R 312 are preferably a substituted or unsubstituted aryl group.

[0371] Also, phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), dimethylphenyl group (each isomer), methylethylphenyl group (each isomer), methylpropylphenyl group (each isomer), methylbutylphenyl group (each isomer), methylpentylphenyl group (each isomer), methylhexylphenyl group (each isomer), methylheptylphenyl group (each isomer), methyloctylphenyl group (each isomer), methylnonylphenyl group (each isomer), methyldecylphenyl group (each isomer), methylundecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyldodecylphenyl group (each isomer), methyltridecylphenyl group (each isomer), diethylphenyl group (each isomer), ethylpropylphenyl group (each isomer), ethylbutylphenyl group (each isomer), ethylpentylphenyl group (each isomer), ethylhexylphenyl group (each isomer), ethylheptylphenyl group (each isomer), ethyloctylphenyl group (each isomer), ethylnonylphenyl group (each isomer), ethyldecylphenyl group (each isomer), ethylundecylphenyl group (each isomer), ethyldodecylphenyl group (each isomer), dipropylphenyl group (each isomer), propylbutylphenyl group (each isomer), propylpentylphenyl group (each isomer), propylhexylphenyl group (each isomer), propylheptylphenyl group (each isomer), propyloctylphenyl group (each isomer), propylnonylphenyl group (each isomer), propyldecylphenyl group (each isomer), propylundecylphenyl group (each isomer), dibutylphenyl group (each isomer), butylpentylphenyl group (each isomer), butylhexylphenyl group (each isomer), butylheptylphenyl group (each isomer), butyloctylphenyl group (each isomer), butylnonylphenyl group (each isomer),Butyldecylphenyl group (each isomer), dipentylphenyl group (each isomer), pentylhexylphenyl group (each isomer), pentylheptylphenyl group (each isomer), pentyloctylphenyl group (each isomer), pentylnonylphenyl group (each isomer), dihexylphenyl group (each isomer), hexylheptylphenyl group (each isomer), hexyloctylphenyl group (each isomer), diheptylphenyl group (each isomer), trimethylphenyl group (each isomer), dimethylethylphenyl group (each isomer), dimethylpropylphenyl group (each isomer), dimethylbutylphenyl group (each isomer), dimethylpentylphenyl group (each isomer), dimethylhexylphenyl group (each isomer), dimethylheptylphenyl group (each isomer), dimethyloctylphenyl group (each isomer), dimethylnonylphenyl group (each isomer), dimethyldecylphenyl group (each isomer), dimethylundecylphenyl group (each isomer), dimethyldodecylphenyl group (each isomer), triethylphenyl group (each isomer), diethylmethylphenyl group (each isomer), diethylpropylphenyl group (each isomer), diethylbutylphenyl group (each isomer), diethylpentylphenyl group (each isomer), diethylhexylphenyl group (each isomer), diethylheptylphenyl group (each isomer), diethyloctylphenyl group (each isomer), diethylnonylphenyl group (each isomer), diethyldecylphenyl group (each isomer), tripropylphenyl group (each isomer), dipropylmethylphenyl group (each isomer), dipropylethylphenyl group (each isomer), dipropylbutylphenyl group (each isomer), dipropylpentylphenyl group (each isomer), dipropylhexylphenyl group (each isomer), dipropylheptylphenyl group (each isomer), dipropyloctylphenyl group (each isomer), tributylphenyl group (each isomer), dibutylmethylphenyl group (each isomer), dibutylethylphenyl group (each isomer), dibutylpropylphenyl group (each isomer), dibutylpentylphenyl group (each isomer), dibutylhexylphenyl group (each isomer), methoxyphenyl group (each isomer), or ethoxyphenyl group (each isomer) is more preferable.,

[0372] Further, a phenyl group, a methoxyphenyl group (each isomer), or an ethoxyphenyl group (each isomer) is more preferable.

[0373] Preferable carbonic acid esters (III-1) include, for example, diphenyl carbonate, bis(2-methoxyphenyl) carbonate, bis(2-ethoxyphenyl) carbonate, and the like.

[0374] [Isocyanate compound] Examples of the isocyanate compound include a compound represented by the general formula (VII) (hereinafter sometimes referred to as "isocyanate compound (VII)") and the like.

[0375] [Chemical formula]

[0376] (In the general formula (VII), R 71 and n71 are the same as R 51 and n51 described above, respectively.)

[0377] R 71 When is an aliphatic hydrocarbon group, specific examples of the isocyanate (VII) include aliphatic diisocyanates, aliphatic triisocyanates, substituted cycloaliphatic polyisocyanates, and the like.

[0378] Examples of the aliphatic diisocyanates include diisocyanatoethane, diisocyanatopropane (each isomer), diisocyanatobutane (each isomer), diisocyanatopentane (each isomer), diisocyanatohexane (each isomer), diisocyanatodecane (each isomer), isophorone diisocyanate (each isomer), dicyclohexylmethane diisocyanate (each isomer), and the like.

[0379] Examples of the aliphatic triisocyanates include triisocyanatohexane (each isomer), 4-isocyanatomethyl-1,8-octamethylene diisocyanate, triisocyanatononane (each isomer), triisocyanatodecane (each isomer), and the like.

[0380] Examples of the substituted cycloaliphatic polyisocyanates include diisocyanatocyclobutane (each isomer), diisocyanatocyclohexane (each isomer), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (at least one of the cis and trans isomers), methylene bis(cyclohexyl isocyanate) (each isomer), and the like.

[0381] R 71 When R is an aromatic group, specific examples of the isocyanate (VII) include aromatic diisocyanates, aromatic triisocyanates, and the like.

[0382] Examples of the aromatic diisocyanates include diisocyanatobenzene (each isomer), diisocyanatotoluene (each isomer), bis(isocyanatophenyl)methane (each isomer), diisocyanatomesitylene (each isomer), diisocyanatobiphenyl (each isomer), diisocyanatodibenzyl (each isomer), bis(isocyanatophenyl)propane (each isomer), bis(isocyanatophenyl)ether (each isomer), bis(isocyanatophenoxyethane) (each isomer), diisocyanatoxylene (each isomer), diisocyanatoanisole (each isomer), diisocyanatophenetole (each isomer), diisocyanatonaphthalene (each isomer), diisocyanatomethylbenzene (each isomer), diisocyanatomethylpyridine (each isomer), diisocyanatomethylnaphthalene (each isomer), diisocyanatodiphenylmethane (each isomer), tetramethylxylylene diisocyanate (each isomer), and the like.

[0383] Examples of aromatic triisocyanates include triisocyanatobenzene (each isomer), triisocyanato-methylbenzene (each isomer), tris(isocyanatopropan-yl)benzene (each isomer), tris(isocyanatopropan-yl)-methylbenzene (each isomer), tris(isocyanatomethyl)-methylbenzene (each isomer), ((isocyanato-phenylene)bis(methylene))bis(isocyanatobenzene) (each isomer), and the like.

[0384] R 71 When R is aromatic, the electron-withdrawing effect of the aromatic group increases the reactivity of the directly bonded isocyanate group. Furthermore, the more isocyanate groups that are directly bonded to the same aromatic compound, the higher the reactivity becomes due to the mutual electron-withdrawing effect. From the viewpoint of reactivity, R 71 Preferably, the number of isocyanate groups is 2 or more, and more preferably 3 or more. On the other hand, when the reactivity of the isocyanate becomes high, reactions with moisture, with other isocyanates, and with other impurities occur, and the stability of the compound at room temperature and when heated decreases. From the viewpoint of the stability of the isocyanate compound, 71 The number of isocyanate groups directly bonded to is preferably 4 or less, and more preferably 3 or less.

[0385] R 71When the aliphatic hydrocarbon group or aromatic group in [it] has 1 to 4 ester groups or nitrogen atoms, specific examples of the isocyanate (VII) include, for example, 2-isocyanato-ethyl acrylate, 2-isocyanato-ethyl 2-methylacrylate, 2-isocyanato-propyl acrylate, 2-isocyanato-propyl 2-methylacrylate, 3-isocyanato-propyl acrylate, 3-isocyanato-propyl 2-methylacrylate, 4-isocyanato-butyl acrylate, 4-isocyanato-butyl 2-methylacrylate, 5-isocyanato-pentyl acrylate, 5-isocyanato-pentyl 2-methylacrylate, 6-isocyanato-hexyl acrylate, 6-isocyanato-hexyl 2-methylacrylate, 8-isocyanato-octyl acrylate, 8-isocyanato-octyl 2-methylacrylate, 10-isocyanato-decyl acrylate, 10-isocyanato-decyl 2-methylacrylate, 11-isocyanato-undecyl acrylate, 11-isocyanato-undecyl 2-methylacrylate, 12-isocyanato-dodecyl acrylate, 12-isocyanato-dodecyl 2-methylacrylate, lysine methyl ester diisocyanate, lysine ethyl ester diisocyanate, 2-isocyanatoethyl-2,5-diisocyanatopentanoate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate, bis(2-isocyanatoethyl)-2-isocyanatobutanedioate, bis(2-isocyanatoethyl)-2-isocyanatopentanedioate, tris(2-isocyanatoethyl)hexane-1,3,6-tricarboxylate, tris(isocyanatoethyl)amine, tris(isocyanatopropyl)amine, and the like.

[0386] The isocyanate compound obtained by the production method of the present embodiment can be suitably used as a production raw material for polyurethane foams, paints, adhesives, etc. By the production method of the present embodiment, an isocyanate compound can be produced in good yield without using highly toxic phosgene.

[0387] [Carbonyl compound (I)] Carbonyl compound (I) is a by-product that is by-produced when the N-substituted carbamate compound in step (2) is thermally decomposed to produce an isocyanate compound. When the compound (I) and a carbonic acid ester react under reaction conditions such as a decrease in temperature under thermal decomposition conditions between a compound having an isocyanate terminal or an N-substituted carbamate terminal, a reaction occurs due to intermolecular interaction, and a reaction in which each terminal group is inserted into the carbonic acid ester skeleton proceeds, whereby the carbonyl compound (I) is considered to be generated. In the production method of the present embodiment, the carbonyl compound (I) acts as a good solvent for a modified product of the isocyanate compound, and the carbonyl compound (I) acts as a terminal blocking agent to suppress the increase in molecular weight of the modified product of the isocyanate compound, thereby suppressing the formation of solids and the increase in liquid viscosity in the production system of the isocyanate compound by the thermal decomposition reaction of the carbamate compound. Further, since the carbonyl compound (I) has a higher boiling point than the isocyanate compound and has fewer crosslinking points than the modified product of the isocyanate compound, it can also act as a solvent during the purification of the isocyanate compound. Alternatively, it binds to a functional group such as a carbodiimide group to prevent the modified products of isocyanate from binding to each other and increasing in molecular weight. By these actions, the operability during the purification of the isocyanate compound is improved, and it becomes possible to recover the isocyanate compound in a high yield.

[0388] Examples of the carbonyl compound (I) include compounds represented by the following general formula (I).

[0389] [Chemical formula]

[0390] (In the general formula (I), R11 is an organic group with a valence of (n11 + n12), and R 12 is a monovalent organic group. n11 is an integer from 1 to 8, n12 is an integer from 0 to 7, and the sum of n11 and n12 is from 2 to 8.)

[0391] (R 11 ) R 11 is an organic group with a valence of (n11 + n12), that is, an organic group with a valence of 2 to 8. Among them, R 11 is preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms and a valence of 2 to 4 or an aromatic hydrocarbon group with 6 to 20 carbon atoms and a valence of 2 to 3, which may contain an ester group of 1 to 4 or a nitrogen atom.)

[0392] R 11 Specifically, examples of R 51 include the same ones as those exemplified as organic groups in the above R

[0393] Among them, R 11 is preferably a group represented by any of the following formulas (Ia-1) to (Ia-28), and more preferably a group represented by formula (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19). In each formula, the wavy line indicates a bond.)

[0394]

Chemical formula

[0395]

Chemical formula

[0396] (R 12 ) R 12 is a monovalent organic group, preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms, which may contain an oxygen atom.)

[0397] R 12 Specifically as the above R 52 Those similar to those exemplified in the above can be mentioned.

[0398] (n11 and n12) n11 represents the number of carbamate groups and is an integer of 1 or more and 8 or less. n12 represents the number of isocyanate groups and is an integer of 0 or more and 7 or less. The sum of n11 and n12 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and even more preferably an integer of 3 or more and 4 or less. When the sum of n11 and n12 is at least the above lower limit value, as the molecular weight of the carbonyl compound increases, the standard boiling point also increases, and the separation from the isocyanate becomes easier. On the other hand, when it is at most the above upper limit value, the modification reaction with the highly reactive isocyanate groups possessed by the isocyanate compound is more suppressed, and the adhesion and clogging to the apparatus can be further reduced.

[0399] Preferred carbonyl compounds (I) include, for example, compounds represented by the following formulas (I-1) to (I-17b). In the following formulas (I-1) to (I-17b), the substituent R' is preferably a phenyl group, (o-, m-, or p-methyl)phenyl group, ethyl group, propyl group (each isomer), or butyl group (each isomer).

[0400]

Chemical formula

[0401]

Chemical formula

[0402] ≪Method for producing carbamate compound≫ The method for producing a carbamate compound according to this embodiment includes a reaction step of reacting a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the presence of an amine compound having no active hydrogen as a catalyst to obtain a carbamate compound.

[0403] In the production method of this embodiment, the reaction for generating a carbamate compound (specifically, N-substituted carbamate) is an equilibrium reaction. However, by using an amine compound having no active hydrogen as a catalyst, the time required to reach equilibrium can be shortened. Thereby, favorable effects such as downsizing of the apparatus and improvement in the selectivity of the carbamate compound due to reduction of side reactions are produced.

[0404] In addition, since the amine compound having no active hydrogen is a non-metal catalyst, it can be easily separated from the reaction mixture by selecting one having an appropriate vapor pressure, and denaturation when obtaining an isocyanate compound from the carbamate compound by thermal decomposition can be suppressed.

[0405] In the production method of this embodiment, as the amine compound having no active hydrogen as a catalyst, any one can be used as long as it is as described later. However, when the vapor pressure of the catalyst is higher than the vapor pressure of the hydroxy compound under the reaction conditions of the above reaction step, it becomes easy to separate and recover the catalyst from the reaction solution containing the hydroxy compound and N-substituted carbamate. On the other hand, when the vapor pressure of the catalyst is lower than the vapor pressure of the hydroxy compound under the reaction conditions of the above reaction step, the concentration of the catalyst in the liquid phase is kept high, which is effective for promoting the reaction.

[0406] Each step of the method for producing a carbamate compound according to this embodiment will be described in detail below.

[0407] <Reaction step: Carbamation reaction step> In the reaction step, a primary amine compound, a carbonic acid derivative, and a hydroxy compound are reacted in the presence of an amine compound having no active hydrogen as a catalyst to obtain a carbamate compound.

[0408] The reaction process preferably includes the following steps (X1) and (X2). From a primary amine compound, a carbonic acid derivative, and a hydroxy compound, in the presence of an amine compound having no active hydrogen as a catalyst, an N-substituted carbamate is produced by a carbamation reaction, and a compound having a carbonyl group derived from the carbonic acid derivative and a hydroxy compound are included, and a gas-phase component containing at least one compound selected from the group consisting of an active hydrogen compound derived from the carbonic acid derivative and an amine compound having no active hydrogen may be recovered, a carbamate synthesis step (step (X1)); A condensation step of the gas-phase component (step (X2)) in which the gas-phase component is condensed by a condenser

[0409] Hereinafter, each of these steps will be described.

[0410] [Step (X1): Carbamate synthesis step] Step (X1) is a carbamate synthesis step in which a primary amine compound, a carbonic acid derivative, and a hydroxy compound are used as raw materials, and in the presence of an amine compound having no active hydrogen as a catalyst, a carbamate compound is produced by a carbamation reaction, and a hydroxy compound and a compound having a carbonyl group derived from the carbonic acid derivative are included, and a gas-phase component containing at least one compound selected from the group consisting of an active hydrogen compound derived from the carbonic acid derivative and an amine compound having no active hydrogen may be recovered.

[0411] Step (X1) is roughly classified into A method of producing an N-substituted carbamate by "simultaneously" reacting a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the presence of at least one amine compound having no active hydrogen as a catalyst (method (1A)); A step (b1) of reacting a primary amine compound and a carbonic acid derivative in the presence or absence of an amine compound having no active hydrogen as a catalyst to produce a carbonyl compound having a group derived from the primary amine compound, and reacting the carbonyl compound with a hydroxy compound in the presence of the amine compound having no active hydrogen to produce an N-substituted carbamate, and a step (b2) of producing an N-substituted carbamate, and a method (method (1B)); Two methods can be carried out.

[0412] The above-mentioned "carbonyl compound having a group derived from the primary amine compound" is a compound produced by the reaction of the primary amine compound and the carbonic acid derivative and represented by the following general formula (XII).

[0413] [Chemical formula]

[0414] (In the general formula, R 121 is a group derived from the primary amine compound, that is, the same as R 21b in the general formula (IIb) described later. R 122 is a group derived from the carbonic acid derivative, that is, the same as R 321 , R 322 , R 323 , or R 324 in the general formula (III-2) described later, the same as R 331 in the general formula (III-3) described later, or the same as R 311b or R 312b in the general formula (III-1b) described later. n121 is the same as n21b in the general formula (IIb) described later.)

[0415] In the production method of the present embodiment, method (1A) and method (1B) may be combined and carried out.

[0416] (Method (1A)) The "simultaneously" in method (1A) means that, while the step of producing the N-substituted carbamate in method (1B) is divided into two steps, the steps in method (1A) are not divided, and it does not necessarily mean that the primary amine compound, the carbonic acid derivative, and the hydroxy compound react completely simultaneously.

[0417] The reaction conditions for producing an N-substituted carbamate by reacting a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the presence of a catalyst vary depending on the compounds to be reacted. The amount of the hydroxy compound used is usually in the range of 1 to 500 times the molar amount of the amino group of the primary amine compound used, with the hydroxyl group of the hydroxy compound being in a stoichiometric ratio. If the amount of the hydroxy compound used is small, it is likely to produce a complexly substituted carbonyl compound, etc. Therefore, it is preferable to use a large excess of the hydroxy compound. Considering the size of the reactor, it is preferably in the range of 1 to 200 times the molar amount, more preferably in the range of 1.5 to 100 times the molar amount, and even more preferably in the range of 2 to 60 times the molar amount.

[0418] The amount of the carbonic acid derivative used (molar amount) is usually in the range of 1 to 100 times the molar amount of the amino group of the primary amine compound, with a stoichiometric ratio. If the amount of the carbonic acid derivative used is small, it is likely to produce a complexly substituted carbonyl compound, etc. Therefore, it is preferable to use an excess amount of the carbonic acid derivative. However, if an excessive amount of the carbonic acid derivative is used, conversely, it is likely to produce a complexly substituted carbonyl compound or unreacted carbonic acid derivative may remain. Therefore, it is preferably in the range of 1.0 to 10 times the molar amount, more preferably in the range of 1.0 to 5 times the molar amount, and even more preferably in the range of 1.05 to 2 times the molar amount.

[0419] The amount (molar amount) of the amine compound having no active hydrogen used as a catalyst may be appropriately adjusted within the range in which the reaction proceeds well. For example, it can be 0.0001 times mol or more and 100 times mol or less, preferably 0.0001 times mol or more and 30 times mol or less, based on the molar amount of the amino group of the primary amine compound.

[0420] The amine compound having no active hydrogen used as a catalyst has a greater promoting effect on the carbamation reaction as the pKa of the conjugate acid is larger. However, when used in a large amount, it may promote the denaturation reaction and conversely reduce the carbamate yield. When using a strong base with a pKa of the conjugate acid of 12 or more, the preferred amount (molar amount) is 0.1 times mol or less, more preferably 0.05 times mol or less, and even more preferably 0.01 times mol or less, based on the molar amount of the amino group of the primary amine compound.

[0421] On the other hand, for a base with a pKa of the conjugate acid of 7 or more and 12 or less, a large amount needs to be used to obtain the same promoting effect as when using the above strong base. Since the promoting effect on the denaturation reaction is smaller than that of the strong base, it can be used in a large amount, but the preferred amount range is 0.5 times mol or more and 30 times mol or less, more preferably 0.5 times mol or more and 10 times mol or less, and even more preferably 1 times mol or more and 3 times mol or less, based on the molar amount of the amino group of the primary amine compound. Also, when using a weak base with a pKa smaller than 7, the preferred amount range is 0.5 times mol or more and 30 times mol or less, more preferably 1 times mol or more and 10 times mol or less, based on the molar amount of the amino group of the primary amine compound.

[0422] The reaction temperature depends on the reactivity of the primary amine compound, carbonic acid derivative, and hydroxy compound used, but is preferably in the range of 100°C or higher and 350°C or lower, more preferably in the range of 120°C or higher and 320°C or lower, and even more preferably in the range of 140°C or higher and 300°C or lower. When the reaction temperature is at or above the lower limit value, the reaction can be accelerated, and the increase in the carbonyl compound with complex substitution can be more effectively suppressed. On the other hand, when the reaction temperature is at or below the upper limit value, the decomposition of the carbonic acid derivative and the accompanying side reactions can be more effectively suppressed, and the dehydrogenation modification of the hydroxy compound or the decomposition reaction and modification reaction of the product N-substituted carbamate can be more effectively suppressed.

[0423] The reaction pressure varies depending on the composition of the reaction system, reaction temperature, reaction apparatus, etc., and can be carried out under reduced pressure, normal pressure, or increased pressure. Usually, it is preferably carried out in the range of 0.01 kPa or higher and 10 MPa or lower (absolute pressure).

[0424] In the process (X1), the reaction for generating the N-substituted carbamate mainly occurs in the liquid phase in many cases. Therefore, it is preferable that the hydroxy compound and the catalyst exist as liquid-phase components under the reaction conditions. On the other hand, as will be described later, since the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative are introduced into the condenser as gas-phase components and condensed in the condenser, it is preferable that the hydroxy compound also exists as a gas-phase component under the reaction conditions. Therefore, the reaction conditions are set such that the catalyst mainly exists as a liquid-phase component and the hydroxy compound exists partly as a liquid-phase component and partly as a gas-phase component. When using a hydroxy composition composed of a plurality of hydroxy compounds, the reaction conditions are set such that at least one kind of hydroxy compound exists as a liquid-phase component. Such reaction conditions (reaction temperature, pressure) are closely related to the properties of the hydroxy compound and the catalyst used, particularly the correlation between temperature and vapor pressure. Therefore, measure or investigate the properties (correlation between temperature and vapor pressure) of the hydroxy compound and the catalyst used and use them as an index for determining the reaction conditions. Incidentally, it is common knowledge to those skilled in the art that the correlation between temperature and the vapor pressure of a substance also varies greatly depending on the purity of the substance, the coexisting compounds, and their amounts. It is obvious that when setting the reaction conditions, not only the properties (correlation between temperature and vapor pressure) of the above-described hydroxy compound and catalyst but also the coexisting compounds and their amounts should be taken into consideration.

[0425] The reaction for forming an N-substituted carbamate from a primary amine compound, a carbonic acid derivative, and a hydroxy compound is an equilibrium reaction. However, when using one or more selected from the group consisting of a urea compound and an N-unsubstituted carbamate as the carbonic acid derivative, the reaction is strongly biased towards the original system. Therefore, in order to increase the yield of the N-substituted carbamate, it is necessary to carry out the reaction while removing the by-produced active hydrogen compound out of the system as much as possible. Preferably, the active hydrogen compound is removed so that the concentration of the active hydrogen compound in the reaction solution is 1000 ppm by mass or less, more preferably 300 ppm by mass or less, still more preferably 100 ppm by mass or less, and particularly preferably 10 ppm by mass or less. Examples of the method for removing the active hydrogen compound include a reactive distillation method, a method using an inert gas, a membrane separation method, an adsorption separation method, etc. For example, the reactive distillation method is a method of separating the active hydrogen compound sequentially generated under the reaction in a gaseous state by distillation. In order to increase the distillation efficiency of the active hydrogen compound, it can also be carried out under the boiling of a solvent or a hydroxy compound. The method using an inert gas is a method of separating the active hydrogen compound sequentially generated under the reaction from the reaction system by entraining it in a gaseous state with an inert gas. As the inert gas, for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane, etc. are used alone or in combination, and a method of introducing the inert gas into the reaction system is preferred. Examples of the adsorbent used in the adsorption separation method include adsorbents such as silica, alumina, various zeolites, and diatomaceous earths that can be used under the temperature conditions at which the reaction is carried out. These methods for removing the active hydrogen compound out of the system may be carried out alone or in combination of a plurality of methods.

[0426] The by-produced active hydrogen compound referred to here includes, for example, an amine compound other than the starting primary amine compound and the amine compound having no active hydrogen which is a catalyst, generated from urea or a substituted urea and an amine compound, and a hydroxy compound other than the solvent generated from a carbonic acid ester and an amine compound.

[0427] The reaction time (retention time in the case of a continuous reaction) varies depending on the composition of the reaction system, reaction temperature, method for removing the active hydrogen compound, reaction apparatus, reaction pressure, etc., but is usually 0.01 hour or more and 100 hours or less. The reaction time can also be determined by the production amount of the target compound, N-substituted carbamate. For example, after sampling the reaction solution, quantifying the content of N-substituted carbamate in the reaction solution, and confirming that it is produced at a yield of 10% by mass or more based on the mass of the raw material primary amine compound used, the reaction may be stopped, or after confirming that the yield is 90% by mass or more, the reaction may be stopped.

[0428] In the carbamation reaction, it is not always necessary to use a reaction solvent, but for the purpose of facilitating the reaction operation, an appropriate solvent, for example, alkanes such as pentane (each isomer), hexane (each isomer), heptane (each isomer), octane (each isomer), nonane (each isomer), decane (each isomer), etc.; aromatic hydrocarbons and alkyl-substituted aromatic hydrocarbons such as benzene, toluene, xylene (each isomer), ethylbenzene, diisopropylbenzene (each isomer), dibutylbenzene (each isomer), mesitylene, paracymene, tetralin, naphthalene, etc.; nitrile compounds such as acetonitrile, benzonitrile, etc.; aromatic compounds substituted by a halogen or nitro group such as chlorobenzene, dichlorobenzene (each isomer), bromobenzene, dibromobenzene (each isomer), chloronaphthalene, bromonaphthalene, nitrobenzene, nitronaphthalene, etc.; polycyclic hydrocarbon compounds such as diphenyl, substituted diphenyl, diphenylmethane, terphenyl, anthracene, dibenzyltoluene (each isomer), etc.; alicyclic hydrocarbons such as cyclohexane, cyclopentane, cyclooctane, ethylcyclohexane, etc.; ketones such as methyl ethyl ketone, acetophenone, etc.; esters such as dibutyl phthalate, dihexyl phthalate, dioctyl phthalate, benzyl butyl phthalate, etc.; Ethers and thioethers such as tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether, diphenyl sulfide; Ketone compounds such as acetone and methyl ethyl ketone; Ester compounds such as ethyl acetate and ethyl benzoate; Sulfoxides such as dimethyl sulfoxide and diphenyl sulfoxide; etc. are preferably used as the reaction solvent. Needless to say, the hydroxy compound used in an excessive amount in the reaction is also preferably used as the reaction solvent.

[0429] The carbamation reaction is carried out in a system having a gas phase containing one or more compounds selected from the group consisting of a hydroxy compound and a compound having a carbonyl group derived from a carbonic acid derivative, and a liquid phase in which the carbamation reaction is carried out, which may contain an active hydrogen compound derived from a carbonic acid derivative and an amine compound having no active hydrogen as a catalyst. Depending on the reaction conditions, the carbamation reaction may also occur in the gas phase, but most of the carbamation reaction is carried out in the liquid phase. At this time, the liquid phase volume content in the reactor in which the carbamation reaction is carried out is preferably 50% by volume or less with respect to the volume of the gas phase. When the carbamation reaction is continuously carried out over a long period of time, polymer-like by-products may be generated due to fluctuations in operating conditions (temperature, pressure, etc.). However, when the liquid phase volume content is large, adhesion and accumulation of such polymer-like by-products to the reactor can be avoided. However, when one or more compounds selected from the group consisting of urea compounds and N-unsubstituted carbamates are used as the carbonic acid derivative, if the liquid phase volume content is too large, the removal efficiency of the by-produced active hydrogen compound deteriorates and the yield of N-substituted carbamate may decrease. Therefore, the liquid phase volume content with respect to the volume of the gas phase is preferably 50% by volume or less, more preferably 30% by volume or less, and even more preferably 20% by volume or less. Here, the liquid phase volume content refers to the liquid phase volume ratio with respect to the gas phase volume in the reaction tank part in the case of a tank-type reactor, the stage below the feed stage (excluding the tower bottom and the reboiler part) in the case of a tower-type reactor, and the capacity of the thin-film evaporator in the case of a thin-film evaporator.

[0430] When carrying out the carbamation reaction, the reactor used is not particularly limited as long as it is a reactor equipped with a condenser, and known reactors can be used. However, one or more reactors selected from the group consisting of tank type and tower type equipped with a condenser are preferably used. There are also no particular restrictions on the material of the reactor, and known materials can be used. For example, glass, stainless steel, carbon steel, Hastelloy, those with a glass lining on the base material, and those with a Teflon (registered trademark) coating can also be used. Among them, SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, instrumentation devices such as flow meters and thermometers, and known process devices such as reboilers, pumps, and condensers may be added. Heating may be by known methods such as steam and heaters, and cooling can also use known methods such as natural cooling, cooling water, and brine.

[0431] In the carbamation reaction, steps such as those described below may be added as necessary. Examples of the steps that can be added include a step of removing the generated active hydrogen compound, a step of purifying the primary amine compound, a step of dissolving the carbonic acid derivative in the hydroxy compound, a step of dissolving the hydroxy compound, a step of separating or purifying the hydroxy compound, a step of purifying the N-substituted carbamate from the generated reaction solution, a step of incinerating or disposing of by-products, etc. Steps and devices within the scope that can be envisioned by those skilled in the art may be added.

[0432] (Method (1B)) Hereinafter, Method (1B) will be described.

[0433] 1. Step (b1) The amount of the hydroxy compound used (in molar amount) and the amount of the amine compound having no active hydrogen used as a catalyst (in molar amount) can be the same as the amounts used in the above Method (1A).

[0434] The amount of the carbonic acid derivative used (in molar amount) is usually in the range of 1 to 100 times the stoichiometric ratio relative to the molar amount of the amino group of the primary amine compound. Even when the amount of the carbonic acid derivative used is small, it is likely to produce a carbonyl compound with a complex substitution, so it is preferable to use an excessive amount of the carbonic acid derivative. On the other hand, if an excessively large amount of the carbonic acid derivative is used, conversely, a carbonyl compound with a complex substitution may be likely to be produced, or unreacted carbonic acid derivative may remain. Therefore, it is preferably in the range of 1.0 to 10 times the molar amount, more preferably in the range of 1.1 to 5 times the molar amount.

[0435] The reaction temperature of step (b1) can usually be carried out in the range of 30°C or higher and 250°C or lower. A high temperature is preferable to increase the reaction rate. On the other hand, at a high temperature, unfavorable reactions (such as decomposition reaction of the carbonic acid derivative and complex side reactions caused thereby) may occur, and a carbonyl compound with a complex substitution may be produced. Therefore, it is preferably in the range of 50°C or higher and 200°C or lower, more preferably in the range of 70°C or higher and 180°C or lower. To keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor for carrying out step (b1).

[0436] The reaction pressure varies depending on the type of compound used, the composition of the reaction system, the reaction temperature, the reaction apparatus, etc., but it is usually preferably carried out in the range of 0.01 kPa or higher and 10 MPa or lower (absolute pressure). Considering the ease of industrial implementation, the range of 0.1 kPa or higher and 5 MPa or lower (absolute pressure) is preferable.

[0437] The reaction time (retention time in the case of the continuous method) is not particularly limited and is usually 0.001 hour or more and 100 hours or less, preferably 0.01 hour or more and 80 hours or less, more preferably 0.1 hour or more and 50 hours or less. Further, the reaction solution can be sampled, and for example, it can be confirmed by liquid chromatography that a desired amount of the carbonyl compound having a group derived from the primary amine compound is produced, and then the reaction can be terminated. Step (b1) is a step of producing the carbonyl compound. However, in step (b1), if a large amount of amino groups derived from the unreacted primary amine compound are present, in step (b2) performed after step (b1), a compound having a ureylene group or the like is produced, and not only does the production amount of the N-substituted carbamate decrease, but adhesion and solidification to the reactor often occur. Therefore, in step (b1), it is preferable to reduce the amount of amino groups derived from the primary amine compound as much as possible. Specifically, the ratio of the number of moles of amino groups derived from the organic amine to the number of moles of carbonyl groups constituting the carbonyl compound having a group derived from the primary amine compound is preferably 0.25 or less, more preferably 0.1 or less, and even more preferably 0.05 or less, and it is preferable to continue the reaction until this ratio is reached.

[0438] The hydroxy compound used in step (b1) may be exactly the same as the hydroxy compound used in step (b2), may be partially the same, or may be different. Among them, for ease of operation, it is preferable that the hydroxy compound used in step (b1) is partially or entirely the same as the hydroxy compound used in step (b2). As will be described below, it is more preferable to carry out the reaction of step (b1) in the presence of an aromatic hydroxy compound, or to add an aromatic hydroxy compound after carrying out the reaction of step (b1) in the presence of an alcohol or an aromatic hydroxy compound.

[0439] The reaction solvents shown here can be used in any amount. However, when an alcohol is used as the reaction solvent, the amount used (molar amount) can be in the range of more than 1-fold molar to less than 100-fold molar in stoichiometric ratio with respect to the molar amount of the amino group of the primary amine compound. In order to improve the fluidity of the reaction solution and allow the reaction to proceed efficiently, it is preferable to use an excess of alcohol with respect to the amino group of the primary amine compound. On the other hand, if too much alcohol is used, there are also drawbacks such as an increase in the size of the reactor. Therefore, the amount used (molar amount) can be in the range of preferably more than 5-fold molar to less than 50-fold molar, more preferably more than 8-fold molar to less than 20-fold molar in stoichiometric ratio with respect to the molar amount of the amino group of the primary amine compound.

[0440] Also, when an aromatic hydroxy compound is used as the reaction solvent in step (b1), the amount used (molar amount) can be in the range of more than 1-fold molar to less than 100-fold molar in stoichiometric ratio with respect to the molar amount of the amino group of the primary amine compound. In order to improve the fluidity of the reaction solution and allow the reaction to proceed efficiently, it is preferable to use an excess of the aromatic hydroxy compound with respect to the amino group of the primary amine compound. On the other hand, if too much aromatic hydroxy compound is used, there are also drawbacks such as an increase in the size of the reactor. Therefore, the amount used (molar amount) can be in the range of preferably more than 2-fold molar to less than 50-fold molar, more preferably more than 3-fold molar to less than 20-fold molar in stoichiometric ratio with respect to the molar amount of the amino group of the primary amine compound.

[0441] Among alcohols and aromatic hydroxy compounds as the hydroxy compound, considering the solubility of the carbonyl compound having a group derived from the primary amine compound to be produced, an aromatic hydroxy compound is preferably used. For example, Japanese Patent Laid-Open No. 6-41045 (Reference 1) describes that polyhexamethylene-urea produced by the reaction of urea and hexamethylenediamine is difficult to dissolve in n-butanol. In this regard, aromatic hydroxy compounds often have excellent solubility for various reaction products.

[0442] When using an aromatic hydroxy compound as the reaction solvent, the aromatic hydroxy compound may be used alone or in admixture with other solvents, provided that the amount of the aromatic hydroxy compound used is within the range of the values described above. Even when adding the aromatic hydroxy compound after carrying out step (b1) in the presence of an alcohol, the aromatic hydroxy compound is used within the above range. In that case, the amount of alcohol used during the reaction in step (b1) is also the amount of alcohol in the above-described stoichiometric ratio with respect to the molar amount of the amino group of the primary amine compound.

[0443] The reactor used when carrying out the reaction of step (b1) is not particularly limited, and known reactors can be used. For example, depending on the reaction method and conditions, known reactors such as a stirred tank, a pressurized stirred tank, a vacuum stirred tank, a tower reactor, a distillation column, a packed column, a thin-film evaporator, a tubular reactor, etc. can be appropriately combined and used. Also, the reaction may be batchwise or continuous flow type, and the reactor may be selected according to each reaction type. From the viewpoint of efficiently carrying out the reaction, the continuous flow type is preferred, and it is often efficient to carry out the reaction by flowing the raw material solution through a tubular flow path (pipe) with a small inner diameter. In that case, the thickness and length of the flow path are important, but they can be appropriately determined by the production amount of the carbonyl compound having a group derived from the primary amine compound, the area of the heat transfer surface with respect to the volume inside the hollow, and the required residence time (reaction time). A single flow path can also share its front part as the supply step and its rear part as the reaction step. In this case, the part where the solution flowing through the flow path can reach the target temperature can be regarded as the reaction step, and the other parts can be regarded as the supply step.

[0444] There are no particular restrictions on the material of the reactor, and known materials can be used. For example, glass, stainless steel, carbon steel, Hastelloy, those with a glass lining on the base material, or those with a Teflon (registered trademark) coating can also be used. Among them, SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, known process devices such as instrumentation equipment like flow meters and thermometers, a mechanism for maintaining pressure, reboilers, pumps, condensers, etc. can be added. Heating can be by known methods such as steam, heaters, etc., and cooling can also use known methods such as natural cooling, cooling water, brine, etc.

[0445] In step (b1), steps as described below can be added as necessary. Examples of addable steps include a step of removing by-produced active hydrogen compounds, a step of purifying the primary amine compound, a step of dissolving a carbonic acid derivative in a hydroxy compound, a step of dissolving a hydroxy compound, a step of separating or purifying a hydroxy compound, a step of purifying a carbonyl compound having a group derived from the primary amine compound from the produced reaction solution, a step of incinerating or disposing of by-products, etc. Steps and devices within the range that those skilled in the art can envision can be added.

[0446] From the perspective of selectively producing a carbonyl compound having a group derived from the primary amine compound in step (b1), it is preferable that an active hydrogen compound derived from the carbonic acid derivative is dissolved to a certain extent in the reaction solution. On the other hand, in step (b2) described below, it is preferable that the active hydrogen compound is removed. Therefore, when using the reaction solution of step (b1) as the raw material for step (b2), it is also a preferable method to separate the active hydrogen compound from the reaction solution in advance. The separation method is not particularly limited. For example, by sending the reaction solution to a depressurized container, the gas phase part and the liquid phase part can be quickly separated, and the liquid phase part containing the carbonyl compound having a group derived from the primary amine compound can be recovered and used.

[0447] When a reaction solvent is used in step (b1), the reaction solvent may be removed from the reaction solution of step (b1) before performing step (b2), or step (b2) may be performed as it is without removal. In particular, it is preferable to directly use the hydroxy compound used as the reaction solvent in step (b1) as part of the hydroxy compound in step (b2).

[0448] 2. Step (b2) Step (b2) is a step of producing an N-substituted carbamate by reacting a carbonyl compound having a group derived from the primary amine compound obtained in step (b1) with a hydroxy compound.

[0449] When a hydroxy compound is used as the reaction solvent in step (b1) and the hydroxy compound is the same as the hydroxy compound in step (b2), step (b2) can be directly performed using the reaction solution obtained in step (b1).

[0450] When the reaction solvent in step (b1) is different from the hydroxy composition in step (b2), a hydroxy compound may be newly added to the reaction solution obtained in step (b1) to perform step (b2). Alternatively, one or more hydroxy compounds may be newly added to the reaction solution obtained in step (b1), and then part or all of the reaction solvent in step (b1) may be separated before performing step (b2). After removing part or all of the reaction solvent in step (b1), a hydroxy compound may be newly added before performing step (b2). The hydroxy compound added here includes at least one hydroxy compound selected from the group consisting of an alcohol represented by the general formula (VIa) described below and an aromatic hydroxy compound represented by the general formula (VIb) described below. The method for separating the reaction solvent used in step (b1) is not particularly limited, and known methods such as distillation separation, membrane separation, and extraction separation can be used, but distillation separation is preferred.

[0451] The hydroxy compound used in step (b2) is preferably an aromatic hydroxy compound represented by the general formula (VIb) described below.

[0452] Before performing step (b2) without using a catalyst in step (b1), a catalyst may be added to the reaction solution of step (b1) and then step (b2) may be performed.

[0453] The reaction conditions for producing an N-substituted carbamate by the reaction of a carbonyl compound having a group derived from a primary amine compound and a hydroxy compound in step (b2) vary depending on the compounds to be reacted. However, the amount (molar amount) of the hydroxy compound used is such that the number of moles of the hydroxy compound is in the range of 1 to 500 times, in stoichiometric ratio, with respect to the number of moles of the carbonyl group of the carbonyl compound used. When the amount of the hydroxy compound is small, carbonyl compounds with complex substitutions or high molecular weight compounds having a carbonyl bond in the molecule are likely to be produced. Therefore, it is preferable to use a large excess of the hydroxy compound. Among them, considering the size of the reactor, the amount (molar amount) of the hydroxy compound used is such that the number of moles of the hydroxy compound is in the range of preferably 1 to 200 times, more preferably 1.5 to 100 times, still more preferably 2 to 60 times, in stoichiometric ratio, with respect to the number of moles of the carbonyl group of the carbonyl compound used.

[0454] The reaction temperature is in the range of 40°C or higher and 380°C or lower, more preferably 50°C or higher and 320°C or lower, still more preferably 60°C or higher and 300°C or lower, particularly preferably 80°C or higher and 300°C or lower, and most preferably 100°C or higher and 280°C or lower, although it depends on the compounds used. When the reaction temperature is at or above the lower limit value, the reaction can be accelerated, and the increase in carbonyl compounds with complex substitutions can be more effectively suppressed. On the other hand, when the reaction temperature is at or below the upper limit value, the decomposition of the carbonic acid derivative and the accompanying side reactions can be more effectively suppressed, and the dehydrogenation modification of the hydroxy compound or the decomposition reaction and modification reaction of the product N-substituted carbamate can be more effectively suppressed.

[0455] The reaction pressure varies depending on the composition of the reaction system, reaction temperature, method for removing the active hydrogen compound derived from the carbonic acid derivative, reaction apparatus, etc. Usually, it is preferably carried out in the range of 0.01 Pa or more and 10 MPa or less (absolute pressure). Considering the ease of industrial implementation, the range of 0.1 Pa or more and 5 MPa or less (absolute pressure) is preferred, and the range of 0.1 Pa or more and 1.5 MPa or less (absolute pressure) is even more preferred.

[0456] In step (b2), the reaction for forming the N-substituted carbamate is often mainly carried out in the liquid phase. Therefore, it is preferable that the hydroxy compound and the catalyst exist as liquid phase components under the reaction conditions. On the other hand, as will be described later, in step (X2), the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative are introduced into the condenser as gas phase components and condensed in the condenser. Therefore, it is preferable that the hydroxy compound also exists as a gas phase component under the reaction conditions. Therefore, the reaction conditions are set such that the catalyst mainly exists as a liquid phase component and the hydroxy compound exists partly as a liquid phase component and partly as a gas phase component. When using a plurality of hydroxy compounds, the reaction conditions are set such that at least one kind of hydroxy compound exists as a liquid phase component. Such reaction conditions (reaction temperature, pressure) are closely related to the properties of the hydroxy compound and the catalyst used, particularly the correlation between temperature and vapor pressure. Therefore, measure or investigate the properties of the hydroxy compound and the catalyst used (the correlation between temperature and vapor pressure) and use it as an index for determining the reaction conditions. Incidentally, it is common knowledge to those skilled in the art that the correlation between temperature and the vapor pressure of a substance also varies greatly depending on the purity of the substance, coexisting compounds, and their amounts. When setting the reaction conditions, it is obvious that not only the properties of the above-mentioned hydroxy compound and catalyst (the correlation between temperature and vapor pressure) but also coexisting compounds and their amounts should be taken into consideration.

[0457] As described above, the reaction for generating N-substituted carbamate is an equilibrium reaction. When using one or more selected from the group consisting of urea compounds and N-unsubstituted carbamate as the carbonic acid derivative, the reaction is largely biased towards the original system. Therefore, in order to increase the yield of N-substituted carbamate, it is necessary to carry out the reaction while removing the by-produced active hydrogen compound out of the system as much as possible. Preferably, the active hydrogen compound is removed so that the concentration of the active hydrogen compound in the reaction solution is 1000 mass ppm or less, more preferably 300 mass ppm or less, still more preferably 100 mass ppm or less, and particularly preferably 10 mass ppm or less. Examples of the method include a reactive distillation method, a method using an inert gas, a membrane separation method, an adsorption separation method, etc. For example, the reactive distillation method is a method of separating the active hydrogen compound sequentially generated under the reaction in a gaseous state by distillation. In order to increase the distillation efficiency of the active hydrogen compound, it can also be carried out under the boiling of a solvent or a hydroxy compound. The method using an inert gas is a method of separating the active hydrogen compound sequentially generated under the reaction from the reaction system by entraining it in a gaseous state with an inert gas. As the inert gas, for example, nitrogen, helium, argon, carbon dioxide gas, methane, ethane, propane, etc. are used alone or in combination, and a method of introducing the inert gas into the reaction system is preferred. Examples of the adsorbent used in the adsorption separation method include adsorbents that can be used under the temperature conditions at which the reaction is carried out, such as silica, alumina, various zeolites, and diatomaceous earths. These methods for removing the active hydrogen compound out of the system may be carried out alone or in combination of multiple methods.

[0458] The reaction time (retention time in the case of a continuous reaction) varies depending on the composition of the reaction system, reaction temperature, method for removing the active hydrogen compound, reaction apparatus, reaction pressure, etc., but is usually 0.01 hour or more and 100 hours or less. The reaction time can also be determined by the production amount of the target compound, N-substituted carbamate. For example, after sampling the reaction solution, quantifying the content of N-substituted carbamate in the reaction solution, and confirming that it is produced at a yield of 10% by mass or more based on the mass of the carbonyl compound having a group derived from the primary amine compound, the reaction may be stopped, or after confirming that the yield is 90% by mass or more, the reaction may be stopped. The yield of N-substituted carbamate is preferably 50% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more based on the mass of the carbonyl compound having a group derived from the primary amine compound.

[0459] In the reaction, it is not always necessary to use a reaction solvent, but an appropriate solvent may be used for the purpose of facilitating the reaction operation, etc. Examples of the reaction solvent include the same ones as those exemplified in method (1A). Needless to say, the hydroxy compound used in an excessive amount in the reaction is also suitably used as the reaction solvent.

[0460] The reaction in step (b2) is carried out in a system having a gas phase containing a hydroxy compound, a compound having a carbonyl group derived from a carbonic acid derivative, and an active hydrogen compound by-produced in the reaction, and a liquid phase in which the reaction in step (b2) is carried out. Most of the reactions in step (b2) are carried out in the liquid phase, but depending on the reaction conditions, the reaction may also occur in the gas phase. In that case, the liquid phase volume content in the reactor in which the reaction in step (b2) is carried out is preferably 50% by volume or less with respect to the volume of the gas phase. When the reaction is continuously carried out over a long period of time, polymer-like by-products may be generated due to fluctuations in operating conditions (temperature, pressure, etc.). However, if the liquid phase volume content in the reactor is large, adhesion and accumulation of such polymer-like by-products to the reactor can be avoided. However, if the liquid phase volume content is too large, the removal efficiency of the by-produced active hydrogen compound may deteriorate and the yield of N-substituted carbamate may decrease. Therefore, the liquid phase volume content with respect to the volume of the gas phase is preferably 50% by volume or less, more preferably 30% by volume or less, and even more preferably 20% by volume or less. Here, the liquid phase volume content refers to the liquid phase volume ratio with respect to the gas phase volume in the reaction tank part in the case of a tank-type reactor, in the part below the feed stage (excluding the bottom of the tower and the reboiler part) in the case of a tower-type reactor, and in the volume of the thin-film evaporator in the case of a thin-film evaporator.

[0461] The reactor used when carrying out the reaction in step (b2) is not particularly limited as long as it is a reactor equipped with a condenser, and a known reactor can be used. However, one or more reactors selected from the group consisting of tank-type and tower-type reactors equipped with a condenser are preferably used.

[0462] As described above, the reaction in step (b2) is carried out in a system having a gas phase containing a hydroxy compound, a compound having a carbonyl group derived from a carbonic acid derivative, and an active hydrogen compound by-produced in the reaction, and a liquid phase in which most of the reaction in step (b2) is carried out. The liquid phase volume content in the reactor in which the reaction in step (b2) is carried out is preferably carried out under the condition of 50% by volume or less with respect to the volume of the gas phase. The reactor for carrying out the reaction in step (b2) is also selected to meet the said condition.

[0463] Specifically, as the reactor, conventionally known reactors such as a stirring tank, a pressurized stirring tank, a depressurized stirring tank, a tower reactor, a distillation column, a packed column, a thin-film evaporator, etc. can be appropriately combined and used. There is no particular limitation on the type of condenser provided in the reactor, and known condensers can be used. For example, conventionally known condensers such as a multi-tube cylindrical condenser, a double-tube condenser, a single-tube condenser, an air-cooled condenser, etc. can be appropriately combined and used. The condenser may be provided inside the reactor, may be provided outside the reactor, or may be connected to the reactor by piping, and various forms are adopted in consideration of the type of the reactor and the condenser, the method of handling the condensate, etc.

[0464] There is also no particular limitation on the materials of the reactor and the condenser, and known materials can be used. For example, those made of glass, stainless steel, carbon steel, Hastelloy, those with glass lining on the base material, or those with Teflon (registered trademark) coating can also be used. Among them, SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, instrumentation devices such as a flow meter and a thermometer, and known process devices such as a reboiler, a pump, and a condenser may be added. Heating may be by known methods such as steam and a heater, and cooling may also use known methods such as natural cooling, cooling water, and brine.

[0465] In step (b2), steps as described below may be added as necessary. Examples of the steps that can be added include, for example, a step of removing the generated active hydrogen compound, a step of purifying the primary amine compound, a step of dissolving the carbonic acid derivative in the hydroxy compound, a step of separating or purifying the hydroxy compound, a step of purifying the carbonyl compound having a group derived from the primary amine compound from the generated reaction solution, a step of incinerating or discarding by-products, etc., and steps and apparatuses within the range that can be assumed by those skilled in the art may be added.

[0466] The N-substituted carbamate obtained by the above reaction is the N-substituted carbamate represented by the general formula (Va) described later when an alcohol is used as the hydroxy compound. When an aromatic hydroxy compound is used as the hydroxy compound, it is the N-substituted carbamate represented by the general formula (Vb) described later.

[0467] In the production method of the present embodiment, in step (X1), the following step (c1) can be further performed. That is, step (X1) may further include the following step (c1). A step (step (c1)) of reacting a compound having at least one functional group selected from the group consisting of a ureylene group and a biuret group with a carbonic acid derivative in the presence of at least one amine compound having no active hydrogen as a catalyst.

[0468] International Publication No. 2014 / 157636 (Reference 2) discloses a method for obtaining an N-substituted carbamate by reacting a compound having at least one functional group selected from the group consisting of a ureylene group (a group represented by the following formula (XIII-1)) and a biuret group (a group represented by the following formula (XIII-2)) generated in the production of an N-substituted carbamate with a carbonic acid derivative. The catalyst suitable for the above step (X1) is also preferably used for the reaction of obtaining an N-substituted carbamate from a compound having at least one functional group selected from the group consisting of a compound having a ureylene group and a biuret group and a carbonic acid derivative.

[0469]

Chemical formula

[0470] (In formulas (XIII-1) and (XIII-2), the wavy line represents a bond and represents the bonding site with the group derived from the primary amine compound.)

[0471] Step (c1) is preferably carried out in the co - presence of a hydroxy compound. The hydroxy compound may be an alcohol represented by general formula (VIa) described below, or may be an aromatic hydroxy compound represented by general formula (VIb) described below.

[0472] The reaction between the compound having a ureylene group represented by the above formula (XIII - 1) and the carbonic acid derivative is preferably carried out at 100°C or higher and 350°C or lower. At a low temperature, the reaction efficiency is poor, while at too high a temperature, a denaturation reaction will occur. Therefore, the reaction is preferably carried out at 120°C or higher and 330°C or lower, more preferably at 140°C or higher and 300°C or lower.

[0473] The amount (molar amount) of the carbonic acid derivative used depends on the type of the carbonic acid derivative and the reaction conditions, but usually, the ratio of the molar number of the carbonic acid derivative to the molar number of the ureylene group of the compound having a ureylene group is 10 or less. To increase the reaction rate and make the reaction efficiency good, a larger amount of the carbonic acid derivative is preferably used. However, if an excessive amount of the carbonic acid derivative is used, side reactions such as N - alkylation may occur. Therefore, the ratio of the molar number of the carbonic acid derivative to the molar number of the ureylene group of the compound having a ureylene group is preferably 5 or less, more preferably 3 or less.

[0474] The amount (molar amount) of the amine compound having no active hydrogen used as a catalyst is not particularly limited. For example, it can be 0.0001 times mol or more and 100 times mol or less, preferably 20 times mol or less, based on the molar amount of the ureylene group of the compound having a ureylene group. When the amine compound having no active hydrogen is an amidine or guanidine which is a strong base, the amount used is preferably 1 times mol or less, more preferably 0.2 times mol or less, still more preferably 0.1 times mol or less, based on the molar amount of the ureylene group.

[0475] The reaction between the compound having a ureylene group and the carbonic acid derivative is preferably carried out in the presence of a solvent. The solvent is not particularly limited as long as it can dissolve the compound having a ureylene group and the carbonic acid derivative and is stable at the reaction temperature, and examples include the same solvents as those described in the above step (X1), alcohols represented by the general formula (VIa) described below, and hydroxy compounds such as aromatic hydroxy compounds represented by the general formula (VIb) described below. In particular, aromatic hydroxy compounds are preferably used.

[0476] Step (c1) may be carried out using the compound having a ureylene group contained in the reaction solution obtained in step (X1) (by-produced in step (X1)) after producing an N-substituted carbamate from a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the above step (X1), or may be carried out simultaneously with the production of an N-substituted carbamate by the reaction of a primary amine compound, a carbonic acid derivative, and a hydroxy compound to produce an N-substituted carbamate by the reaction of the by-produced compound having a ureylene group and a carbonic acid derivative. In such a case, the solvent used in step (X1) or the hydroxy compound used in excess can also be used as the solvent.

[0477] The reaction may be carried out under any conditions of pressurization, normal pressure, or reduced pressure. The reaction is preferably carried out in an inert gas atmosphere such as nitrogen, argon, helium, or neon.

[0478] As the reaction apparatus, conventionally known reactors such as a stirring tank, a pressure-type stirring tank, a reduced-pressure stirring tank, a tower-type reactor, a distillation column, a packed column, and a thin-film evaporator can be appropriately combined and used. A known cooling device and heating device may be installed to keep the reaction temperature constant. There is no particular limitation on the material, and known materials can be used. For example, those made of glass, stainless steel, carbon steel, Hastelloy, those with a glass lining on the base material, or those with a Teflon (registered trademark) coating can also be used.

[0479] <Step (X2): Condensation step of gas-phase components> Step (X2) is a condensation step of condensing a gas-phase component that may contain at least one selected from the group consisting of a carbonic acid derivative and a compound having a carbonyl group derived from the carbonic acid derivative recovered in Step (X1) and a hydroxy compound, and may contain one compound selected from the group consisting of an active hydrogen compound derived from the carbonic acid derivative and an amine compound having no active hydrogen which is a catalyst, by a condenser provided in a reactor for carrying out the carbamate synthesis step (Step (X1)).

[0480] There is no particular limitation on the type of the condenser, and a known condenser can be used. For example, a conventionally known condenser such as a multi-tube cylindrical condenser, a double-tube condenser, a single-tube condenser, an air-cooled condenser, etc. can be used in appropriate combination. The condenser may be provided inside the reactor, may be provided outside the reactor, or may be connected to the reactor by piping, and various forms are adopted in consideration of the type of the reactor and the condenser, the method of handling the condensate, etc.

[0481] There is also no particular limitation on the materials of the reactor and the condenser, and known materials can be used. For example, those made of glass, stainless steel, carbon steel, Hastelloy, those with glass lining on the base material, or those with Teflon (registered trademark) coating can also be used. Among them, SUS304, SUS316, SUS316L, etc. are inexpensive and can be preferably used. If necessary, instrumentation devices such as a flow meter and a thermometer, and known process devices such as a reboiler, a pump, and a condenser may be added. Heating may be by a known method such as steam or a heater, and cooling may also be by a known method such as natural cooling, cooling water, or brine.

[0482] In Step (X2), if necessary, steps and devices within the range that those skilled in the art can assume may be added.

[0483] The production method of this embodiment is a method for producing an N-substituted carbamate by subjecting a primary amine compound, a carbonic acid derivative, and a hydroxy compound to a carbamation reaction using a reactor equipped with a condenser in the presence of an amine compound having no active hydrogen as a catalyst. In the carbamation reaction, one or more selected from the group consisting of a carbonic acid derivative and a compound having a carbonyl group derived from the carbonic acid derivative, and a hydroxy compound are included, and a gas phase component may be generated which contains one compound selected from the group consisting of an active hydrogen compound derived from the carbonic acid derivative and an amine compound having no active hydrogen as a catalyst.

[0484] In step (X2), this gas phase component is introduced into a condenser provided in the reactor that performs the carbamation step (step (1)), and a part or all of the hydroxy compound, a part or all of one or more selected from the group consisting of a carbonic acid derivative and a compound having a carbonyl group derived from the carbonic acid derivative, and a part or all of the amine compound having no active hydrogen as a catalyst are condensed. At this time, the molar amount of the hydroxy compound to be condensed is preferably 1 molar equivalent or more, more preferably 2 molar equivalents or more, and still more preferably 3 molar equivalents or more in a stoichiometric ratio with respect to the molar amount of the compound having a carbonyl group derived from the carbonic acid derivative to be condensed.

[0485] In the process (X2), the "compound having a carbonyl group derived from a carbonic acid derivative" listed as a component to be condensed in the condenser is a compound having a carbonyl group derived from a carbonic acid derivative used in the reaction of a primary amine compound, a carbonic acid derivative, and a hydroxy compound. The compounds having a carbonyl group derived from a carbonic acid derivative include the carbonic acid derivative itself used as a raw material (one or more selected from the group consisting of unreacted substances and excess amounts when used in excess with respect to the primary amine compound), a compound obtained by reacting the carbonic acid derivative with a hydroxy compound, and a compound obtained by reacting the carbonic acid derivative. Although it is difficult to identify all of the compounds having a carbonyl group derived from a carbonic acid derivative, specific compounds include the carbonic acid derivative used as a raw material, by-products such as urea compounds such as isocyanic acid, biuret, and isocyanurate, N-unsubstituted carbamate in which the carbamate group is a group derived from a hydroxy compound, and carbonate in which the ester group is a group derived from a hydroxy compound. The compound having a carbonyl group derived from urea can be quantified by a method of detecting the carbonyl group contained in the compound by a method such as infrared spectroscopy, near-infrared spectroscopy, Raman spectroscopy, or ultraviolet spectroscopy. Alternatively, it can also be quantified by a method of specifically analyzing the generated compound by a method such as gas chromatography, liquid chromatography, or NMR. Many of these compounds having a carbonyl group derived from a carbonic acid derivative have a high melting point and tend to precipitate. Among the above-mentioned compounds having a carbonyl group derived from a carbonic acid derivative, urea in particular requires the most attention because its production amount (detected amount) is large and its melting point is 135°C.

[0486] In the condensation operation, by setting the molar amount of the hydroxy compound to be condensed to be equal to or greater than the lower limit value with respect to the molar amount of the compound having a carbonyl group derived from the carbonic acid derivative to be condensed, these mixtures can be made into a uniform liquid mixture in the condenser. Therefore, not only is the handling of the mixture facilitated, but also problems such as the adhesion and accumulation of solid components on the condenser can be avoided. In order to set the molar amount of the hydroxy compound to be condensed within the above range, the condenser is preferably maintained at a temperature 90 °C or more lower than the standard boiling point of the hydroxy compound and at a temperature at which the hydroxy compound does not solidify.

[0487] The mixture of the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative condensed by the above condenser may be circulated inside the reactor and reused for the reaction of the primary amine compound, the carbonic acid derivative, and the hydroxy compound, or one or more selected from the group consisting of the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative may be recovered from the mixture and reused for the reaction of the primary amine compound, the carbonic acid derivative, and the hydroxy compound, or it may be reused in the step of producing the N-unsubstituted carbamate (referring to the above step (c1)).

[0488] When reusing the condensation components, the amount of the active hydrogen compound derived from the carbonic acid derivative contained in the mixture of the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative is preferably 5000 mass ppm or less, more preferably 3000 ppm or less, and even more preferably 2000 ppm or less with respect to the mass of the mixture.

[0489] Even if the active hydrogen compound exceeding the above upper limit value is contained, it can be reused in the reaction of the primary amine compound, the carbonic acid derivative, and the hydroxy compound. However, as described above, the reaction of the primary amine compound, the carbonic acid derivative, and the hydroxy compound is an equilibrium reaction. In order to efficiently proceed the reaction, it is necessary to remove the active hydrogen compound, which is a by-product, out of the system. Therefore, by setting the amount of the active hydrogen compound in the mixture to be equal to or less than the above upper limit value, the amount of the active hydrogen compound extracted in the reaction can be made smaller, and it is possible to more effectively prevent the introduction of the active hydrogen compound in excess of the amount of the active hydrogen compound that can be extracted per unit time (depending on the capacity of the urethane production reactor, reaction conditions, etc.). The concentration of the active hydrogen compound in the reaction solution can be reduced to a preferable range (the range described above), and the yield of the N-substituted carbamate can be further improved. Further, although it is preferable that the amount of the active hydrogen compound in the mixture is small, by setting it to be equal to or less than the above upper limit value, it is not necessary to exert much labor to minimize the amount of the active hydrogen compound.

[0490] As described above, various compounds may be recovered as the compound having a carbonyl group derived from the carbonic acid derivative. However, even if the mixture of the hydroxy compound and the compound having a carbonyl group derived from the carbonic acid derivative contains these compounds, it does not interfere with the reuse of the condensed components.

[0491] Next, the raw materials and products used in the method for producing the carbamate compound of the present embodiment will be described in detail below.

[0492] <Amine compound having no active hydrogen> As the amine compound having no active hydrogen, those having at least one functional group selected from the group consisting of a tertiary amino group, a nitrogen-containing aromatic group, an amidine group, and a guanidine group are preferably used.

[0493] An amine compound having no active hydrogen and used as a catalyst preferably has a pKa of the conjugate acid of 6 or more and 17 or less, more preferably has one or more functional groups selected from the group consisting of a tertiary amino group, an amidine group, and a guanidine group and a pKa of 10 or more and 15 or less, and still more preferably has one or more functional groups selected from the group consisting of an amidine group and a guanidine group and a pKa of 12 or more and 15 or less, from the viewpoint of the promoting effect on the carbamation reaction.

[0494] On the other hand, an amine compound having too high basicity tends to promote the modification reaction of carbamate, and the carbamate yield may decrease due to the modification. Therefore, from the viewpoint of suppressing the modification, an amine compound having no active hydrogen and used as a catalyst preferably has a pKa of 1 or more and 15 or less, more preferably has one or more functional groups selected from the group consisting of a tertiary amino group and a nitrogen-containing aromatic group and a pKa of 3 or more and 12 or less, and still more preferably has a nitrogen-containing aromatic group and a pKa of the conjugate acid of 4 or more and 7 or less.

[0495] [Compound having a tertiary amino group] The "tertiary amino group" in the present specification is a group represented by the formula (XIV). In the formula (XIV), the wavy line means a bond and represents the bonding site with a monovalent organic group.

[0496] [Chemical formula]

[0497] The total carbon number constituting the compound having a tertiary amino group is preferably 3 or more and 85 or less, more preferably 3 or more and 30 or less. The number of tertiary amino groups contained in the compound having a tertiary amino group is preferably 1 or more and 6 or less, more preferably 1 or more and 3 or less.

[0498] Preferred amine compounds having a tertiary amino group include Aromatic organic mono-tertiary amines such as N,N-dimethylaniline, N,N-diethylaniline, N-methyl-N-ethylaniline, N,N-dimethylaminopyridine; Aromatic organic poly-tertiary amines such as N,N,N’,N’-tetramethylphenylenediamine (each isomer), methylenebis(N,N-dimethylaniline) (each isomer); Aliphatic mono-tertiary amines such as triethylamine, ethyldiisopropylamine, N-methylmorpholine, N-methylpiperidine, quinuclidine; Aliphatic poly-tertiary amines such as N,N’-dimethylpiperazine, triethylenediamine, N,N,N’ N’-tetramethylethylenediamine, N,N,N’ N’-tetramethylhexanediamine, N,N,N’ N’-tetramethylxylylenediamine, pentamethyldiethylenetriamine, bis(2-morpholinoethyl) ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine, hexamethylenetetramine; And the like.

[0499] [Compound having a nitrogen-containing aromatic group] As used herein, the "nitrogen-containing aromatic group" refers to a heteroaromatic group in which at least one nitrogen atom is included in the atoms constituting the heteroaromatic ring. A compound having a nitrogen-containing aromatic group is composed of non-metal atoms (carbon, oxygen, nitrogen, sulfur, silicon), and the total number of atoms thereof is preferably 5 or more and 85 or less, more preferably 6 or more and 30 or less. The non-metal atoms are preferably selected from carbon, oxygen and nitrogen, and more preferably carbon atoms. The total number of carbon atoms constituting the compound having a nitrogen-containing aromatic group is preferably 3 or more and 85 or less, more preferably 3 or more and 30 or less. In addition, the number of nitrogen-containing aromatic groups contained in the compound having a nitrogen-containing aromatic group is preferably 1 or more and 5 or less, more preferably 1 or more and 3 or less.

[0500] Preferred nitrogen-containing aromatic groups include a pyridyl group, an imidazolyl group, a pyrazolyl group, a quinolyl group, an isoquinolyl group, an oxazolyl group, a thiazolyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, etc., any of which may have a substituent.

[0501] Examples of amine compounds having a preferred nitrogen-containing aromatic group include pyridine, picoline (each isomer), lutidine (each isomer), collidine (each isomer), 1-methylimidazole, 1-methylpyrazole, quinoline, isoquinoline, methylquinoline (each isomer), oxazole, thiazole, pyridazine, pyrimidine, pyrazine, etc.

[0502] [Compound having an amidine group] As the compound having an amidine group, a compound represented by the general formula (VIII-1) is preferably used.

[0503] [Chemical formula]

[0504] (In the general formula (VIII-1), R 811 , R 812 , R 813 , and R 814 are each independently a monovalent organic group. R 811 and R 812 , R 812 and R 813 , R 813 and R 814 , R 814 and R 811 may each independently be bonded to each other to form a ring structure. The total number of carbon atoms of R 811 , R 812 , R 813 , and R 814 is 5 or more and 85 or less.)

[0505] R 811 , R 812 , R 813 , and R 814Examples of the monovalent organic group include aliphatic groups, aromatic groups, groups formed by bonding aliphatic and aromatic groups, and groups in which the above groups are bonded via a covalent bond with a specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon), and the like.

[0506] R 811 and R 812 、R 812 and R 813 、R 813 and R 814 、R 814 and R 811 are each independently and may be bonded to each other to form a ring structure together with a nitrogen atom.

[0507] The total number of carbon atoms constituting the compound having an amidine group is 5 or more and 85 or less, preferably 5 or more and 30 or less.

[0508] Further, the compound having an amidine group preferably has one or more ring structures.

[0509] The number of amidine groups contained in the compound having an amidine group is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less.

[0510] Preferred compounds having an amidine group include 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo-[5.4.0]undec-7-ene (DBU), 1,5-diazabicyclo-[4.3.0]nona-5-ene (DBN), and the like.

[0511] [Compound having a guanidine group] As the compound having a guanidine group, a compound represented by the following general formula (VIII-2) is preferably used.

[0512]

Chemical formula

[0513] (In general formula (VIII-2), R 821 、R822 , R 823 , R 824 , and R 825 are each independently a monovalent organic group. R 821 and R 822 , R 822 and R 823 , R 823 and R 824 , R 824 and R 825 , R 825 and R 821 are each independently bonded to each other to form a ring structure, if desired. R 821 , R 822 , R 823 , R 824 , and R 825 The total number of carbon atoms of is 5 or more and 85 or less. )

[0514] R 821 , R 822 , R 823 , R 824 , and R 825 Examples of the monovalent organic group in include, for example, an aliphatic group, an aromatic group, a group formed by bonding an aliphatic group and an aromatic group, and a group in which the above group is bonded via a covalent bond with a specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon), etc.

[0515] R 821 and R 822 , R 822 and R 823 , R 823 and R 824 , R 824 and R 825 , R 825 and R 821 are each independently bonded to each other to form a ring structure together with a nitrogen atom, if desired.

[0516] The total number of carbon atoms constituting the compound having a guanidine group is 5 or more and 85 or less, preferably 5 or more and 30 or less.

[0517] Also, the number of guanidine groups contained in the compound having a guanidine group is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less.

[0518] Examples of the compound having a preferable guanidine group include pentamethylguanidine, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, and the like.

[0519] <Primary amine compound> The "primary amine compound" in this specification refers to the "primary amine" (mono-primary amine and poly-primary amine) defined in Nomenclature Rule C-8 defined by IUPAC. Such a primary amine compound is a compound represented by the following general formula (IIb) (hereinafter, may be referred to as "primary amine compound (IIb)").

[0520]

Chemical formula

[0521] (In general formula (IIb), R 21b is an organic group with a valence of n21b. n21b is an integer of 1 or more and 10 or less.)

[0522] R 21b The organic group in represents an aliphatic group, an aromatic group, or a group formed by bonding an aliphatic group and an aromatic group, and represents an acyclic hydrocarbon group, or a cyclic hydrocarbon group (for example, a monocyclic hydrocarbon group, a condensed polycyclic hydrocarbon group, a bridged cyclic hydrocarbon group, a spiro hydrocarbon group, a ring assembly hydrocarbon group, a cyclic hydrocarbon group with a side chain, a heterocyclic group, a heterocyclic spiro group, a heterobridged cyclic group, a complex heterocyclic group), a group formed by bonding an acyclic hydrocarbon group and a cyclic hydrocarbon group, and a group in which these groups are bonded via a covalent bond with a specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon). Further, the covalent bond with the above specific non-metal atom means, for example, a state in which the above-described group is bonded via a covalent bond with one or more groups selected from the group consisting of the groups represented by the following formulas (IIb-a1) to (IIb-a10).

[0523]

Chemical formula

[0524] R 21b As for R, considering the difficulty of side reactions occurring, it is a group formed by bonding an aliphatic group, an aromatic group, or a group formed by bonding an aliphatic group and an aromatic group, and is an acyclic hydrocarbon group, or a cyclic hydrocarbon group (monocyclic hydrocarbon group, condensed polycyclic hydrocarbon group, bridged cyclic hydrocarbon group, spiro hydrocarbon group, ring assembly hydrocarbon group, cyclic hydrocarbon group with a side chain), and a group formed by bonding an acyclic hydrocarbon group and a cyclic hydrocarbon group (groups substituted with each other), preferably a group having 1 to 85 carbon atoms, more preferably a group having 1 to 70 carbon atoms in consideration of fluidity, etc., and even more preferably a group having 1 to 13 carbon atoms.

[0525] R 21b Preferred aliphatic groups in R are those having 5 to 70 carbon atoms, which are a chain hydrocarbon group, a cyclic hydrocarbon group, and a group formed by bonding a chain hydrocarbon group and a cyclic hydrocarbon group (for example, referring to a cyclic hydrocarbon group substituted with a chain hydrocarbon group, a chain hydrocarbon group substituted with a cyclic hydrocarbon group, etc.).

[0526] Specific examples of preferred primary amine compounds are as follows: 1) R 21b is an aromatic group having 6 to 85 carbon atoms which may be substituted with one or more groups selected from the group consisting of an aliphatic group and an aromatic group, and n21b is 1, an aromatic primary monoamine compound; 2) R 21b is a group having 6 to 85 carbon atoms containing one or more aromatic rings which may be substituted with one or more groups selected from the group consisting of an aliphatic group and an aromatic group, n21b is 2 or more, and an aromatic primary polyamine compound in which the aromatic group in R 21b is substituted with an NH2 group; 3) R 21b is an aliphatic primary (mono or poly)amine compound which is an aliphatic group having 1 to 85 carbon atoms and may be substituted with an aromatic group. That's it.

[0527] In the above, an atom (preferably a carbon atom) to which an NH2 group is bonded and which is contained in an aromatic ring is referred to as an aromatic amine compound, and the case where it is bonded to an atom that is not an aromatic ring (mainly carbon) is referred to as an aliphatic amine compound.

[0528] Among them, as the primary amine compound, an aromatic primary polyamine compound or an aliphatic primary polyamine compound is preferable.

[0529] Specific examples of preferable primary amine compounds are shown below.

[0530] [Aromatic primary monoamine compound] A preferable aromatic primary monoamine compound is a compound represented by the following general formula (IIb-1).

[0531] [Chemical formula]

[0532] (In general formula (IIb-1), ring A 211b is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. R 211b is a hydrogen atom, or an alkyl group, a cycloalkyl group, an aryl group which may be substituted with an aromatic group, or a group bonded via a covalent bond between these groups and a specific non-metal atom (carbon, oxygen, nitrogen, sulfur, silicon). R 211b may combine with ring A 211b to form a ring structure. Further, n211b is an integer of 1 or more and 10 or less.)

[0533] (A 211b ) Ring A 211b is an aromatic hydrocarbon ring having 6 to 20 carbon atoms....

Claims

1. A step (1) of reacting a primary amine compound with a carbonic acid derivative and extracting a compound having a boiling point lower than that of the N-substituted carbamate compound produced as a by-product to obtain an N-substituted carbamate compound; A step (2) of thermally decomposing the N-substituted carbamate compound in the presence of an aprotic solvent using the reaction solution containing the N-substituted carbamate compound obtained in the step (1), and extracting the hydroxy compound produced as a by-product to obtain an isocyanate compound; A step (3) of separating the isocyanate compound and the aprotic solvent from the reaction solution containing the isocyanate compound obtained in the step (2); A step (4) of purifying the isocyanate compound by removing components having a boiling point higher than that of the isocyanate compound from the fraction containing the isocyanate compound obtained in the step (3); comprising: In the step (1), reacting a primary amine compound with urea or a urea derivative as the carbonic acid derivative in the presence of a hydroxy compound, and extracting a compound having a boiling point lower than that of the N-substituted carbamate compound produced as a by-product to obtain an N-substituted carbamate compound, or reacting a primary amine compound with a carbonic acid ester as the carbonic acid derivative, and extracting a hydroxy compound as a compound having a boiling point lower than that of the N-substituted carbamate compound produced as a by-product to obtain an N-substituted carbamate compound, wherein the carbonic acid derivative is urea, a carbonic acid ester or a urea derivative represented by the following general formula (IV), A method for producing an isocyanate compound, wherein the N-substituted carbamate compound is a compound represented by the following general formula (V). 【Chemical 1】 (In the general formula (IV), R41 is a hydrogen atom or an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms.) [Chemical Formula 2] (In the general formula (V), n51 is 2 or more and 4 or less, and R51 is a divalent to tetravalent aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms which may have 1 or more and 4 or less ester groups or nitrogen atoms, or a divalent to trivalent aromatic group having 6 or more and 20 or less carbon atoms which may have 1 or more and 4 or less ester groups or nitrogen atoms.)

2. The method for producing an isocyanate compound according to claim 1, further comprising a step (5) of hydrolyzing a fraction containing the aprotic solvent separated in the step (3) or a component having a boiling point higher than that of the isocyanate compound removed in the step (4) in the coexistence of an alkali and water to obtain the primary amine compound and the hydroxy compound.

3. The method for producing an isocyanate compound according to claim 1 or 2, wherein in the step (2), a liquid phase containing the isocyanate compound is obtained while extracting the by-produced hydroxy compound into the gas phase.

4. The method for producing an isocyanate compound according to claim 1 or 2, wherein the step (1) and the step (2) are carried out using one or more reactors selected from the group consisting of a tank reactor, a distillation column, a tubular evaporator, a thin-film evaporator, and a falling-film evaporator.

5. The method for producing an isocyanate compound according to claim 1 or 2, wherein at least one of the step (1) and the step (2) is carried out by a reactive distillation method.

6. The method for producing an isocyanate compound according to claim 1 or 2, wherein the hydroxy compound extracted in the step (2) is circulated to the step (1) and reused.

7. The method for producing an isocyanate compound according to claim 1 or 2, wherein the aprotic solvent separated in the step (3) is circulated to the step (2) and reused.

8. The method for producing an isocyanate compound according to claim 1 or 2, wherein the aprotic solvent is a carbonic acid ester.

9. The method for producing an isocyanate compound according to claim 1 or 2, wherein in the step (4), the isocyanate compound is purified in the presence of a carbonyl compound represented by the following general formula (I) in an amount of 1 mass ppm or more and 50 mass% or less based on the mass of the fraction containing the isocyanate compound. 【Chemical 3】 (In the general formula (I), R １１ is an aliphatic hydrocarbon group having 2 to 4 valences and 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 2 to 3 valences and 6 to 20 carbon atoms, which may have an ester group or a nitrogen atom of 1 to 4, or R １２ is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms which may contain an oxygen atom. n11 is an integer of 1 to 4, n12 is an integer of 0 to 3, and the sum of n11 and n12 is an integer of 2 to 4.)

10. The method for producing an isocyanate compound according to claim 1 or 2, wherein the primary amine compound is a compound represented by the following general formula (II). [Chemical Formula 4] (In the general formula (II), R ２１ is an organic group having 3 to 85 carbon atoms, an aliphatic hydrocarbon group having 3 to 30 carbon atoms, an aromatic hydrocarbon group, or a group formed by bonding an aliphatic hydrocarbon group and an aromatic hydrocarbon group. n21 is an integer of 2 or more.)

11. The method for producing an isocyanate compound according to claim 10, wherein n21 is 3 or more.

12. The method includes a reaction step of reacting a primary amine compound, a carbonic acid derivative, and a hydroxy compound in the presence of an amine compound having no active hydrogen as a catalyst to obtain a carbamate compound. The amine compound having no active hydrogen is N,N'-dimethylaniline, N,N'-diethylaniline, N-methyl-N'-ethylaniline, N,N'-dimethylaminopyridine, N,N,N',N'-tetramethylphenylenediamine, methylenebis(N,N'-dimethylaniline), triethylamine, ethyldiisopropylamine, N-methylmorpholine, N-methylpiperidine, quinuclidine, N,N'-dimethylpiperazine, triethylenediamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylhexanediamine, N,N,N',N'-tetramethylxylylenediamine, pentamethyldiethylenetriamine, bis(2-morpholinoethyl)ether, hexahydro-1,3,5-tris(3-dimethylaminopropyl)-1,3,5-triazine, or hexamethylenetetramine, The amine compound having no active hydrogen is pyridine, picoline, lutidine, collidine, 1-methylimidazole, 1-methylpyrazole, quinoline, isoquinoline, methylquinoline, oxazole, thiazole, pyridazine, pyrimidine, or pyrazine, The amine compound having no active hydrogen is an amidine group-containing compound, and the amidine group-containing compound is 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine, 1,8-diazabicyclo-[5.4.0]undec-7-ene, or 1,5-diazabicyclo-[4.3.0]nona-5-ene, The amine compound having no active hydrogen is a guanidine group-containing compound, and the guanidine group-containing compound is pentamethylguanidine, or 7-methyl-1,5,7-triazabicyclo[4.4.0]deca-5-ene, The method for producing a carbamate compound, wherein the carbonic acid derivative is urea, a carbonic acid ester, or a urea derivative represented by the following general formula (IV). 【Chemical Formula 5】 (In the general formula (IV), R41 is a hydrogen atom or an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms.)

13. The method for producing a carbamate compound according to claim 12, wherein the primary amine compound is an aliphatic or aromatic primary polyamine compound.

14. The method for producing a carbamate compound according to claim 12, wherein the hydroxy compound is an aromatic hydroxy compound.

15. A method for producing an isocyanate compound, comprising a thermal decomposition step of thermally decomposing a carbamate compound obtained by the method for producing a carbamate compound according to any one of claims 12 to 14.

16. A method for recovering an amine compound represented by the following general formula (IIa) from a liquid phase component containing a compound having a boiling point higher than that of the isocyanate compound by-produced in the method for producing an isocyanate compound represented by the following general formula (VIIa), comprising a step (a) of reacting the liquid phase component, an aromatic hydroxy compound, an active hydrogen-containing compound, and a catalyst in a reactor to obtain a reaction liquid containing the amine compound represented by the general formula (IIa), wherein the step (a) includes the following steps (a1) and (a2), a step (a1) of mixing the liquid phase component and an aromatic hydroxy compound; a step (a2) of reacting the mixture obtained in the step (a1), an active hydrogen-containing compound, and a catalyst in a reactor to obtain a reaction liquid containing the amine compound represented by the general formula (IIa), wherein the step (a2) includes the following steps (a2-1) and (a2-2), a step (a2-1) of mixing the mixture obtained in the step (a1), an amine compound as an active hydrogen-containing compound, and a catalyst; a step (a2-2) of reacting the mixture obtained in the step (a2-1) and water as an active hydrogen-containing compound in a reactor to obtain a reaction liquid containing the amine compound represented by the general formula (IIa), further comprising the following steps (b) and (c), a step (b) of separating the amine compound represented by the general formula (IIa) from the reaction liquid containing the amine compound represented by the general formula (IIa); a step (c) of purifying the amine compound represented by the general formula (IIa), further comprising the following step (d), a step (d) of recycling the amine compound represented by the general formula (IIa) purified in the step (c) as a raw material in the method for producing an isocyanate compound represented by the general formula (VIIa), a recovery method further comprising the following steps (e) and (f). a step (e) of separating a hydroxy compound from the reaction liquid containing the amine compound represented by the general formula (IIa); a step (f) of purifying the hydroxy compound 【Chemical Formula 6】 (In general formula (VIIa), R ７１ａ is an aliphatic hydrocarbon group having 1 to 4 ester groups or nitrogen atoms and having 1 to 20 carbon atoms and a valence of 2 to 4, or an aromatic hydrocarbon group having 6 to 20 carbon atoms and a valence of 2 to 3. n71a is an integer of 2 to 4.) 【Chemical Formula 7】 (In the general formula (IIa), R ２１ａ is an aliphatic hydrocarbon group having 1 to 4 ester groups or nitrogen atoms and having 2 to 4 valences and 1 to 20 carbon atoms, or an aromatic hydrocarbon group having 2 to 3 valences and 6 to 20 carbon atoms, and the relational expression: R ２１ａ = R ７１ａ is satisfied. n21a is an integer of 2 or more and 4 or less, and the relational expression: n21a = n71a is satisfied.)

17. The recovery method according to claim 16, wherein the active hydrogen-containing compound is water.

18. The recovery method according to claim 16, wherein the active hydrogen-containing compound is water and a primary amine compound.

19. The recovery method according to claim 18, wherein the primary amine compound is an amine compound represented by the general formula (IIa).

20. In the method for producing an isocyanate compound represented by the general formula (VIIa), a carbonic acid derivative, a hydroxy compound, and an amine compound represented by the general formula (IIa) are used as raw materials, The recovery method according to claim 16, wherein the carbonic acid derivative is urea, a carbonic acid ester, or a urea derivative represented by the following general formula (IV). 【Chemical 8】 (In the general formula (IV), R41 is a hydrogen atom or an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms.)

21. The liquid phase component is a reaction liquid containing a carbamate compound formed from a carbonic acid derivative, a hydroxy compound, and an amine compound represented by the general formula (IIa), and is subjected to a thermal decomposition reaction. When a composition containing the isocyanate compound represented by the general formula (VIIa) thus produced is supplied to a distillation apparatus and the isocyanate compound represented by the general formula (VIIa) is separated as a gas phase component, it is a liquid phase component withdrawn from the distillation apparatus, The recovery method according to claim 16, wherein the carbonic acid derivative is urea, a carbonic acid ester, or a urea derivative represented by the following general formula (IV). 【Chemical Formula 9】 (In the general formula (IV), R41 is a hydrogen atom or an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms.)

22. The recovery method according to claim 16, wherein the liquid phase component contains a compound having one or more functional groups selected from the group consisting of a group represented by the following formula (IX-1), a group represented by the following formula (IX-2), a group represented by the following formula (IX-3), a group represented by the following formula (IX-4), a group represented by the following formula (IX-5), a group represented by the following formula (IX-6), a group represented by the following formula (IX-7), a group represented by the following formula (IX-8), a group represented by the following formula (IX-9), a group represented by the following formula (IX-10), a group represented by the following formula (IX-11), and a group represented by the following formula (IX-12). 【Chemical Formula 10】 (In the formulas (IX-1) to (IX-12), the wavy line indicates a bond.)

23. The recovery method according to claim 22, wherein the liquid-phase component contains a compound having two or more functional groups selected from the group consisting of a group represented by the formula (IX-1), a group represented by the formula (IX-2), a group represented by the formula (IX-3), a group represented by the formula (IX-4), a group represented by the formula (IX-5), a group represented by the formula (IX-6), a group represented by the formula (IX-7), a group represented by the formula (IX-8), a group represented by the formula (IX-9), a group represented by the formula (IX-10), a group represented by the formula (IX-11), and a group represented by the formula (IX-12).

24. The recovery method according to claim 16, wherein the catalyst is at least one compound selected from the group consisting of hydroxides and oxides of alkali metals, hydroxides and oxides of alkaline earth metals, tertiary amine compounds, metal oxides of Group 12, metal oxides of Group 13, and metal oxides of Group 14.

25. The recovery method according to claim 24, wherein the catalyst is at least one compound selected from the group consisting of hydroxides and oxides of alkali metals and hydroxides and oxides of alkaline earth metals.

26. The recovery method according to claim 25, wherein the catalyst is hydroxides and oxides of alkali metals.

27. The recovery method according to claim 16, further comprising the following step (g). Step (g) of reusing the hydroxy compound purified in step (f) as a raw material in the method for producing an isocyanate compound represented by the general formula (VIIa).

28. The recovery method according to claim 16, further comprising the following step (h). Step (h) of reusing at least one residual liquid selected from the group consisting of the residual liquid after separating the amine compound represented by the general formula (IIa) in step (b), the residual liquid after purifying the amine compound represented by the general formula (IIa) in step (c), the residual liquid after separating the hydroxy compound in step (e), and the residual liquid after purifying the hydroxy compound in step (f) in step (a).

29. Distilling and purifying an isocyanate composition, and continuously recovering an isocyanate compound as a gas-phase component, wherein the isocyanate composition is the isocyanate compound, and a carbonyl compound represented by the following general formula (I), A modified product of an isocyanate compound, in which a part of the isocyanate groups of the isocyanate compound is converted into one or more functional groups selected from the group consisting of an isocyanurate group, a carbodiimide group, a uretonimine group, and an allophanate group, wherein the isocyanate compound and the carbonyl compound are different compounds, wherein the value of {3 × (molar amount of isocyanurate group) + 2 × (molar amount of carbodiimide group) + 3 × (molar amount of uretonimine group) + 2 × (molar amount of allophanate group)} ÷ (molar amount of carbonyl compound) is 0.001 or more and 8.0 or less, A method for producing an isocyanate compound. 【Chemical 11】 (In General Formula (I), R11 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms and optionally having 1 to 4 ester groups or nitrogen atoms, or a divalent to trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, R12 is a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms and optionally containing an oxygen atom. n11 is an integer of 1 to 4, n12 is an integer of 0 to 3, and the sum of n11 and n12 is an integer of 2 to 4.)

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