Carbonyl compound, method for producing carbonyl compound, method for producing isocyanate compound, and isocyanate composition

Abstract

The present application provides a carbonyl compound represented by the following general formula (I), wherein R 11 is an organic group having a valence of (n11+n12), and R 12 is an organic group having a valence of 1. 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.

Description

Technical Field

[0001] This invention relates to carbonyl compounds, methods for manufacturing carbonyl compounds, methods for manufacturing isocyanate compounds, and isocyanate compositions. Background Technology

[0002] Isocyanates are widely used as raw materials in the manufacture of polyurethane foams, coatings, adhesives, and more. The main industrial method for manufacturing isocyanates is the reaction of amine compounds with phosgene (phosgene process), and almost all of the world's production is done through the phosgene process. However, the phosgene process has many problems.

[0003] First, phosgene is used extensively as a raw material. Phosgene is extremely toxic, and its handling requires extreme care to prevent worker exposure. Specialized equipment is also needed for waste removal. Second, the phosgene process generates large quantities of the highly corrosive byproduct hydrogen chloride, necessitating a process to remove it. Furthermore, the resulting isocyanates often contain hydrolyzable chlorine. Therefore, using isocyanates produced via the phosgene process can sometimes negatively impact the weather resistance and heat resistance of polyurethane products.

[0004] Against this backdrop, a method for manufacturing isocyanate compounds without using phosgene is desired. As one method for manufacturing isocyanate compounds without using phosgene, a method by thermal decomposition of urethane compounds has been proposed in the literature. The preparation of isocyanates and hydroxyl compounds by thermal decomposition of urethane compounds is previously known (see, for example, Non-Patent Literature 1). The basic reaction is illustrated by the following formula (A).

[0005] [Chemistry 1]

[0006] R(NHCOOR')a→R(NCO)a+aR'OH (A)

[0007] (In formula (A), R is an organic group with a valence of α, R' is an organic group with a valence of 1, and α is an integer greater than or equal to 1.)

[0008] On the other hand, in the thermal decomposition reaction of urethane compounds, various irreversible side reactions are easily generated, such as undesirable thermal modification reactions of the urethane compounds or condensation reactions of isocyanates generated from the thermal decomposition. Examples of such side reactions include, for instance, the reaction that forms an isocyanurate group as represented by formula (B), the reaction that forms a carbodiimide as represented by formula (C), the reaction that forms a urea-ketimine group as represented by formula (D), and the reaction that forms a ureocarbamate group as represented by formula (E) (see, for example, Non-Patent Literature 1-4, etc.).

[0009] [Chemistry 2]

[0010]

[0011] (In equations (B) to (E), R) a ~R h Each of these is an organic group that is independently monovalent.

[0012] Polyurethanes containing urethane bonds are mainly manufactured through the reaction of isocyanates with two or more functional groups with alcohols with two or more functional groups. They are polymers with excellent tensile strength, abrasion resistance, and oil resistance, and are used in a wide range of fields, including flexible foams, rigid foams, elastomers, adhesives, coatings, and bonding agents. Among these, polyurethanes using chain-like or cyclic aliphatic isocyanates as raw materials exhibit excellent weather resistance and lightfastness, and are used in applications requiring high-quality appearance, such as paints for baking, automotive clear coats, and coil coatings.

[0013] As isocyanates, diisocyanates, which are difunctional isocyanates, are used in most cases. However, for the purpose of improving the physical properties of polyurethane or suppressing vapor pressure to ensure the safety of operators, diisocyanates are sometimes polymerized to produce isocyanate polymers, for example, by reactions represented by formulas (a) to (c) below. It should be noted that in the formulas, R represents a divalent organic group, and R' represents a trivalent organic group.

[0014] [Chemistry 3]

[0015]

[0016] The reaction represented by formula (a) above yields an isocyanurate-type isocyanate polymer, the reaction represented by formula (b) above yields a biuret-type isocyanate polymer, and the reaction represented by formula (c) above yields a urethane-type isocyanate polymer. Isocyanurate-type isocyanate polymers have been disclosed in Patent Documents 1-4. Biuret-type isocyanate polymers have been disclosed in Patent Documents 5-10. Urea-type isocyanate polymers have been disclosed in Patent Documents 11 and 12.

[0017] As mentioned above, in applications requiring high-quality appearance, minimal coloring of the polyurethane is desirable. Therefore, it is important not only that the polyurethane polymerization reaction itself is colorless, but also that the raw material isocyanate (isocyanates with two or more functional groups) exhibits minimal coloring. However, isocyanates are typically oxidized by oxygen in the air, making them prone to deterioration or coloring. Furthermore, when isocyanate polymers are manufactured through the polymerization of diisocyanates, there is a tendency for isocyanate coloring to occur due to the action of catalysts or solvents used in the polymerization reaction.

[0018] As methods to suppress the coloring of isocyanates, there are methods of manufacturing and storing them by sealing them with nitrogen gas to isolate them from air; and methods of storing them by adding ultraviolet absorbers, antioxidants, etc. For example, Patent Document 13 discloses a method of treating isocyanates with peroxides after modification in order to manufacture polyisocyanates for light-colored polyurethane paints. In addition, Patent Document 14 studies a method of producing isocyanates with reduced coloring by contacting ozone-containing gas with coloring isocyanates. Furthermore, Patent Document 15 studies a method of producing isocyanates with reduced coloring by irradiating coloring isocyanates with light of wavelengths of 200 to 600 nm.

[0019] Existing technical documents

[0020] Patent documents

[0021] Patent Document 1: US Patent No. 4,324,879

[0022] Patent Document 2: US Patent No. 4,412,073

[0023] Patent Document 3: Japanese Patent Application Publication No. 57-047319

[0024] Patent Document 4: Japanese Patent Application Publication No. 63-057577

[0025] Patent Document 5: US Patent No. 3,976,622

[0026] Patent Document 6: US Patent No. 4,176,132

[0027] Patent Document 7: US Patent No. 4,290,969

[0028] Patent Document 8: US Patent No. 4,837,359

[0029] Patent Document 9: US Patent No. 4,983,762

[0030] Patent Document 10: U.S. Patent No. 5,641,851

[0031] Patent Document 11: Specification of British Patent No. 994890

[0032] Patent Document 12: Japanese Patent Application Publication No. 7-304724

[0033] Patent Document 13: Japanese Patent Application Publication No. 2-228317

[0034] Patent Document 14: Japanese Patent Application Publication No. 8-291129

[0035] Patent Document 15: Japanese Patent Publication No. 2012-506465

[0036] Non-patent literature

[0037] Non-patent document 1: Dritter Jahrgang, "186.AWHofmann: Ueber die aromatischenCyanate.", Berchte der Deutechen Chemischen Gesellschaft, Vol.3, pp.653-658, 1870.

[0038] Non-patent literature 2: Dyer E et al., “Thermal Degradation of Alkyl N-Phenylcarbomates.”, Journal of American Chemical Society, Vol. 81, pp. 2138-2143, 1959.

[0039] 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.

[0040] 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, Perkintransactions II, Vol. 2, pp. 395-402, 1995. Summary of the Invention

[0041] The problem that the invention aims to solve

[0042] The aforementioned side reactions not only lead to a decrease in the yield and selectivity of the target isocyanate compound, but also, particularly in the production of polyisocyanates, cause issues such as the precipitation of polymeric solids and reactor blockage, making long-term operation difficult. Furthermore, in addition to the compounds generated by these side reactions, compounds with higher boiling points than the isocyanate compounds may also be generated; this is currently unknown.

[0043] The present invention was made in view of the above circumstances, and aims to provide novel carbonyl compounds and methods for manufacturing the same, as well as methods for manufacturing isocyanate compounds using the above-described carbonyl compounds.

[0044] In addition, as mentioned above, various methods have been studied to suppress the coloring of isocyanates. In the method of preservation by adding compounds that are not needed in the polymerization reaction to the isocyanate, the added compounds may become the cause of coloring during the manufacture of polyurethanes, etc.

[0045] Furthermore, in the methods disclosed in Patent Documents 4-6, it cannot be said that the coloring has been sufficiently reduced, and it is expected that the coloring of the isocyanate will be further reduced. In addition, distillation purification is a common method for purifying compounds, but since the isocyanate is heated during distillation purification, the coloring of the isocyanate may be intensified, or the isocyanate may be modified.

[0046] The present invention was made in view of the above circumstances, and aims to provide an isocyanate composition in which coloring is sufficiently suppressed and preservation stability is excellent.

[0047] Methods for solving problems

[0048] That is, the present invention includes the following methods.

[0049] (1) Carbonyl compounds represented by the following general formula (I).

[0050] [Chemistry 4]

[0051]

[0052] (In general formula (I), R) 11 For organic groups with a valence of (n11+n12), R 12 An organic group with a monovalent oxidation state. n11 is an integer between 1 and 8, n12 is an integer between 0 and 7, and the sum of n11 and n12 is an integer between 2 and 8.

[0053] (2) The carbonyl compound as described in (1), wherein,

[0054] The above R 11It can have one or more but no more than four ester groups or nitrogen atoms, and be a divalent or quadrivalent aliphatic hydrocarbon group with one or more but no more than 20 carbon atoms, or a divalent or trivalent aromatic hydrocarbon group with six or more but no more than 20 carbon atoms.

[0055] The above R 12 It is an aromatic hydrocarbon group with a monovalent carbon number of 6 to 20 that can contain oxygen atoms.

[0056] (3) The carbonyl compound as described in (1) or (2), wherein,

[0057] The above R 11 It can be an aliphatic hydrocarbon group with 5 to 15 carbon atoms and a valence of 2 to 4, or an aromatic hydrocarbon group with 6 to 15 carbon atoms and a valence of 2 to 3.

[0058] The above R 12 It is an aromatic hydrocarbon group with a carbon number of 6 to 15 and containing oxygen atoms, and has a monovalent oxidation state.

[0059] The above n 11 It is an integer greater than 1 and less than 4.

[0060] The above n 12 It is an integer greater than 0 and less than 3, and

[0061] The above n 11 With n 12 The sum is an integer greater than 2 and less than 4.

[0062] (4) A method for manufacturing a carbonyl compound, which is a method for manufacturing a carbonyl compound according to any one of (1) to (3), wherein the method includes the following steps:

[0063] The carbonyl compound described above is synthesized by mixing one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds with one or more compounds selected from the group consisting of carbonate compounds and hydroxyl compounds and heating the mixture.

[0064] (5) The manufacturing method as described in (4), wherein the isocyanate compound is a compound represented by the following general formula (II).

[0065] [Chemistry 5]

[0066]

[0067] (In general formula (II), R) 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11(where n21 is an integer greater than 2 and less than 8, satisfying the relation: n21 = n11 + n12.)

[0068] (6) The manufacturing method as described in (4) or (5), wherein the above-mentioned carbamate compound is a compound represented by the following general formula (III).

[0069] [Chemistry 6]

[0070]

[0071] (In general formula (III), R) 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 Let n31 be an integer greater than or equal to 1 and less than or equal to 8, and n32 be an integer greater than or equal to 0 and less than or equal to 7. The sum of n31 and n32 is an integer greater than or equal to 2 and less than or equal to 8, satisfying the relation: n31 + n32 = n11 + n12.

[0072] (7) The manufacturing method as described in any one of (4) to (6), wherein the carbonate is a compound represented by the following general formula (IV).

[0073] [Chemistry 7]

[0074]

[0075] (In general formula (IV), R) 41 and R 42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 。 )

[0076] (8) The manufacturing method as described in any one of (4) to (7), wherein the hydroxyl compound is a compound represented by the following general formula (V).

[0077] [Chemistry 8]

[0078] R 51 -OH (V)

[0079] (In general formula (V), R) 51 For a monovalent organic group, the following relationship is satisfied: R 51 =R 12 。 )

[0080] (9) A method for manufacturing an isocyanate compound, comprising the following steps:

[0081] In the presence of any one of the carbonyl compounds in (1) to (3), the reaction solution containing the isocyanate compound represented by the following general formula (II) is purified by distillation to continuously recover the above-mentioned isocyanate compound as a gas phase component.

[0082] [Chemistry 9]

[0083]

[0084] (In general formula (II), R) 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 (where n21 is an integer greater than 2 and less than 8, satisfying the relation: n21 = n11 + n12.)

[0085] (1) An isocyanate composition, wherein,

[0086] Relative to the total mass of the isocyanate composition, it contains:

[0087] Isocyanate compounds of 97% or more by mass; and

[0088] 2.0 ppm or more, 1.0 × 10 4 Carbonyl compounds represented by the following general formula (I) in the mass fraction below ppm,

[0089] The isocyanate compounds mentioned above are different from the carbonyl compounds mentioned above.

[0090] [Chemistry 10]

[0091]

[0092] (In general formula (I), R) 11 For organic groups with a valence of (n11+n12), R 12 An organic group with a monovalent oxidation state. n11 is an integer between 1 and 8, n12 is an integer between 0 and 7, and the sum of n11 and n12 is an integer between 2 and 8.

[0093] (2) The isocyanate composition as described in (1), wherein,

[0094] The above R 11 It can have one or more but no more than four ester groups or nitrogen atoms, and be a divalent or quadrivalent aliphatic hydrocarbon group with one or more but no more than 20 carbon atoms, or a divalent or trivalent aromatic hydrocarbon group with six or more but no more than 20 carbon atoms.

[0095] The above R 12 It is an aromatic hydrocarbon group with a monovalent carbon number of 6 to 20 that can contain oxygen atoms.

[0096] (3) The isocyanate composition as described in (1) or (2), wherein the isocyanate compound is a compound represented by the following general formula (II).

[0097] [Chemistry 11]

[0098]

[0099] (In general formula (II), R) 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 (where n21 is an integer greater than 2 and less than 8, satisfying the relation: n21 = n11 + n12.)

[0100] (4) The isocyanate composition according to any one of (1) to (3), wherein, relative to the total mass of the above isocyanate composition, it further contains 1.0 × 10⁻¹⁰ ppm or more by mass. 4 The compounds selected from the group consisting of carbamate compounds and carbonates with a mass of less than ppm are one or more compounds.

[0101] (5) The isocyanate composition as described in (4), wherein the carbamate compound is a compound represented by the following general formula (III).

[0102] [Chemistry 12]

[0103]

[0104] (In general formula (III), R) 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 Let n31 be an integer greater than or equal to 1 and less than or equal to 8, and n32 be an integer greater than or equal to 0 and less than or equal to 7. The sum of n31 and n32 is an integer greater than or equal to 2 and less than or equal to 8, satisfying the relation: n31 + n32 = n11 + n12.

[0105] (6) The isocyanate composition as described in (4) or (5), wherein the carbonate is a compound represented by the following general formula (IV).

[0106] [Chemistry 13]

[0107]

[0108] (In general formula (IV), R) 41 and R42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 。 )

[0109] The effects of the invention

[0110] The carbonyl compounds and their manufacturing methods described above can provide novel carbonyl compounds.

[0111] The method for producing isocyanate compounds described above, using the carbonyl compound described above, can prevent the solidification of byproducts on the apparatus during the production of isocyanate compounds, and can improve the yield of isocyanate compounds.

[0112] Furthermore, the isocyanate composition according to the above method can provide an isocyanate composition in which coloring is sufficiently suppressed and storage stability is excellent. Attached Figure Description

[0113] Figure 1 This is a schematic diagram illustrating the configuration of an apparatus for manufacturing the carbamate compound used in the examples.

[0114] Figure 2 This is a schematic diagram illustrating the configuration of the thermal decomposition reaction apparatus used in the embodiments.

[0115] Figure 3 This is a schematic diagram illustrating the configuration of the light-boiling separation apparatus used in the embodiments.

[0116] Figure 4 This is a schematic diagram illustrating the configuration of the high-boiling separation apparatus used in the embodiments.

[0117] Figure 5 This is a diagram showing the NMR spectra of the carbamate compounds (I-1a) to (I-1c) prepared in Examples 1-1.

[0118] Figure 6A This is a diagram showing the NMR spectra of the carbamate compounds (I-3a) to (I-3c) prepared in Examples 1-7.

[0119] Figure 6B This is a graph showing the results of gas chromatography-mass spectrometry of the carbamate compounds (I-3a) to (I-3c) prepared in Examples 1-7. Detailed Implementation

[0120] The following describes suitable embodiments of the present invention. It should be noted that the present invention is not limited to the following embodiments, and can be implemented in various ways within the scope of its key points.

[0121] In this specification, when referring to the IUPAC rules and the nomenclature rules prescribed by IUPAC as shown below (except where IUPAC recommendations from other years are specifically cited), it refers to the "Nomenclature of Organic and Biochemical Chemicals" (revised 2nd edition, published by Nan'edo Publishing, Japan, 1992). This version is based on the version published in 1980 as a supplement to "Chemistry" based on Recommendations 1979, which included all rules and Japanese translations of organic and biochemical rules, and incorporates all subsequent revisions and recommendations. "Organic" refers to the general group of compounds that are the object of the nomenclature disclosed in this specification. This object can be the object described in the recommendation proposed in 1993. Among the "organic" compounds that are the object of the aforementioned nomenclature, organometallic compounds and metal complexes are also included. In this embodiment, unless otherwise specified, terms such as "organic group" and "substituent" refer to groups composed of atoms that do not contain metal atoms and / or half-metals. Furthermore, in this embodiment, it is preferable to use an "organic compound", "organic group" or "substituent" 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).

[0122] The terms "aliphatic" and "aromatic" are frequently used in the following description. According to the IUPAC rules mentioned above, organic compounds are classified as aliphatic and aromatic compounds. Aliphatic compounds refer to those defined according to the 1995 IUPAC recommendation regarding the group composition of aliphatic compounds. This recommendation defines aliphatic compounds as "Acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds." Furthermore, the term "aliphatic compound" used in this embodiment refers to any of the following: saturated or unsaturated, chain-like or cyclic. It refers to an "organic compound," "organic group," or "substituent" composed of atoms selected from the group consisting 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).

[0123] When aromatic groups such as aralkyl groups are bonded to aliphatic groups, they are sometimes referred to as "aliphatic groups substituted with aromatic groups" or "groups composed of aliphatic groups bonded with aromatic groups." This is because, based on the reactivity in this embodiment, the properties related to the reaction with groups such as aralkyl groups are very similar to the reactivity of aliphatic groups rather than aromaticity. Additionally, non-aromatic reactive groups containing aralkyl, alkyl, etc., are sometimes referred to as "aliphatic groups that may be substituted with aromatic groups" or "aliphatic groups that may be bonded with aromatic groups," etc.

[0124] It should be noted that when describing the general formulas of compounds used in this specification, the definitions according to the nomenclature rules specified in IUPAC above are used; however, the names of specific groups and illustrative compounds may sometimes use conventional names. Furthermore, in this specification, the number of atoms, substituents, and their quantities are all expressed as integers.

[0125] In this specification, "active hydrogen" refers to hydrogen atoms (excluding aromatic hydroxyl groups) bonded to oxygen, sulfur, nitrogen, silicon, etc., as well as hydrogen atoms in terminal methylene groups. Examples of "active hydrogen" include hydrogen atoms contained in radicals such as -OH, -C(=O)OH, -C(=O)H, -SH, -SO3H, -SO2H, -SOH, -NH2, -NH-, -SiH, and -C≡CH.

[0126] It should be noted that alcohols and aromatic hydroxyl compounds can be cited as examples of compounds containing hydroxyl (-OH) groups.

[0127] In this specification, "alcohol" refers to "compounds in which a hydroxy group, -OH, is attached to asaturated carbonatom (R3COH)" as defined in IUPAC (Rule C-201), excluding aromatic hydroxy compounds in which the hydroxy group is attached to an aromatic ring.

[0128] In this specification, "aromatic hydroxy compounds" refers to phenols as defined in IUPAC (Rule C-202), which are "compounds having one or more hydroxy groups attached to a benzene or other arene ring."

[0129] Carbonyl Compounds

[0130] The carbonyl compound in this embodiment is the compound represented by the following general formula (I) (hereinafter, sometimes referred to as "carbonyl compound (I)").

[0131] [Chemistry 14]

[0132]

[0133] (In general formula (I), R) 11 For organic groups with a valence of (n11+n12), R 12 An organic group with a monovalent oxidation state. n11 is an integer between 1 and 8, n12 is an integer between 0 and 7, and the sum of n11 and n12 is an integer between 2 and 8.

[0134] The inventors discovered that the carbonyl compound (I) is generated during the thermal decomposition reaction of urethane compounds to produce isocyanate compounds. Furthermore, they discovered that the coexistence of this carbonyl compound (I) during the thermal decomposition of urethane compounds to produce isocyanate compounds prevents the solidification of byproducts with higher boiling points than the isocyanate compounds (hereinafter sometimes referred to as "high-boiling-point byproducts") on the equipment in the thermal decomposition and refining processes, and effectively recovers the isocyanate compounds, thereby increasing the yield of the isocyanate compounds, thus completing the present invention.

[0135] [R 11 ]

[0136] R 11 It is an organic group with a valence of (n11+n12), that is, an organic group with a valence of more than 2 but less than 8. Among them, as R... 11 Preferably, it can have one or more ester groups or less than four nitrogen atoms, and be aliphatic hydrocarbon groups with a carbon number of 1 or more than 20 and a valence of 2 to 4 or a valence of 6 to 20 or a valence of 2 to 3 or a valence of 3.

[0137] As R 11 The aliphatic hydrocarbon group in the group is preferably an alkylene or alkane trimethyl group, a cycloalkyl group, a cycloalkylene or cycloalkane trimethyl group, or a group composed of the above-mentioned alkyl group, the above-mentioned alkylene or alkane trimethyl group and the above-mentioned cycloalkyl group, the above-mentioned cycloalkylene or cycloalkane trimethyl group, more preferably a straight-chain or branched alkylene or alkane trimethyl group, a cycloalkylene or cycloalkane trimethyl group, or a group composed of the above-mentioned alkylene or alkane trimethyl group and the above-mentioned cycloalkyl group, the above-mentioned cycloalkylene or cycloalkane trimethyl group.

[0138] Examples of linear or branched alkylene compounds include methylene, ethylene, propylene, trimethylene, pentylene, n-hexene, and decamethylene.

[0139] Examples of cycloalkyl groups include cyclobutylene and cyclohexylene.

[0140] Examples of straight-chain or branched alkane trimethyl groups include hexane trimethyl, nonane trimethyl, and decane trimethyl.

[0141] Examples of cycloalkane trimethyl groups include cyclopropane trimethyl groups, cyclobutane trimethyl groups, cyclopentane trimethyl groups, and cyclohexane trimethyl groups.

[0142] As R 11 The aromatic hydrocarbon group in the group is preferably a substituted or unsubstituted aromatic ring having 6 to 13 carbon atoms. Examples of substituents include alkyl, aryl, and aralkyl groups. The aromatic ring can be an aromatic hydrocarbon ring or an aromatic heterocycle; specifically, examples include benzene rings, naphthalene rings, and pyridine rings.

[0143] R 11 When the aliphatic hydrocarbon group or aromatic group in the compound has one or more but less than four ester groups, it is considered as R. 11 Preferably, the group is formed by reacting the carboxyl group of an amino acid with a hydroxyl compound to obtain an amine compound having an ester group, and removing the terminal primary amino group of the amine compound having an ester group to obtain the group.

[0144] Specifically, examples of amine compounds containing an ester group, as mentioned here, include 2-aminoethyl acrylate, 2-methyl-2-aminoethyl acrylate, 2-aminopropyl acrylate, 2-methyl-2-aminopropyl acrylate, 3-aminopropyl acrylate, 2-methyl-3-aminopropyl acrylate, 4-aminobutyl acrylate, 2-methyl-4-aminobutyl acrylate, 5-aminopentyl acrylate, 2-methyl-5-aminopentyl acrylate, 6-aminohexyl acrylate, 2-methyl-6-aminohexyl acrylate, 8-aminooctyl acrylate, and 2-methyl-8-aminooctyl acrylate. Esters, 10-aminodecyl acrylate, 2-methyl-10-aminodecyl acrylate, 11-aminoundecyl acrylate, 2-methyl-11-aminoundecyl acrylate, 12-aminododecyl acrylate, 2-methyl-12-aminododecyl acrylate, lysine methyl ester diamine, lysine ethyl ester diamine, 2-aminoethyl-2,5-diaminovalerate, 2-aminoethyl-2,6-diaminohexanoate, bis(2-aminoethyl)-2-aminosuccinate, bis(2-aminoethyl)-2-aminopentanoate, tris(2-aminoethyl)hexane-1,3,6-tricarboxylate, etc.

[0145] Examples of amino acids used in the manufacture of amine compounds containing ester groups include lysine, alanine, arginine, asparagine, glutamine, glycine, aspartic acid, glutamic acid, ornithine, histidine, isoleucine, leucine, methionine, phenylalanine, tryptophan, and valine. Among these, lysine, arginine, glycine, aspartic acid, glutamic acid, or ornithine are preferred as amino acids, and lysine, arginine, glycine, aspartic acid, or glutamic acid are more preferred.

[0146] Hydroxyl compounds used in the manufacture of amine compounds having ester groups include alcohols and aromatic hydroxy compounds.

[0147] Examples of alcohols include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotonol, 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, glycerol, trimethylolpropane, pentaerythritol, ethanolamine, propanolamine (1-amino-2-propanol), diethanolamine, diethanolamine, dipropanolamine, 1-amino-2-butanol, etc.

[0148] Examples of aromatic hydroxyl compounds include monophenols such as phenol (carbolic acid), 2-methoxyphenol, cresol, xylenol, carvacrol, thymol, and naphthol, as well as polyphenols such as catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, and resorcinol.

[0149] R 11 When the aliphatic hydrocarbon group or aromatic group in the R group has one or more but less than four nitrogen atoms, it is considered as R 11Preferably, the organic group is the organic group remaining after removing the terminal amino group from an amine compound having one or more secondary or tertiary amines other than the terminal aliphatic hydrocarbon group or aromatic group. Specifically, examples of amine compounds having one or more secondary or tertiary amines other than the terminal aliphatic hydrocarbon group or aromatic group include 2-(dimethylamino)ethyleneamine, 2-(diethylamino)ethyleneamine, 2-(diisopropylamino)ethyleneamine, 2-(cyclohexylamino)ethyleneamine, 3-(cyclohexylamino)propylamine, 3-(diethylamino)propylamine, 3-(dimethylamino)propylamine, diethylenetriamine, diisopropyltriamine, bis-(3-aminopropyl)methyleneamine, 3-(2-aminoethylamino)propylamine, N,N'-bis(3-aminopropyl)ethylenediamine, 1-(3-aminopropyl)imidazole, triaminoethylamine, triaminopropylamine, etc. Among them, the preferred amine compound is an amine compound having one or more but no more than two tertiary amines other than the terminal and having an aliphatic hydrocarbon group or an aromatic group, and more preferably an amine compound having one tertiary amine other than the terminal and having an aliphatic hydrocarbon group or an aromatic group.

[0150] Among them, as R 11 Preferably, the group is represented by any one of the formulas (Ia-1) to (Ia-24) below, and more preferably by the group represented by formulas (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18), or (Ia-19). It should be noted that in each formula, the wavy line represents a connecting bond.

[0151] [Chemistry 15]

[0152]

[0153] [Chemistry 16]

[0154]

[0155] [R 12 ]

[0156] R 12 The organic group is monovalent, preferably an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms that can contain oxygen atoms.

[0157] As R 12Aliphatic hydrocarbon groups in the group can include, for example, methyl, ethyl, propyl (various isomers), butyl (various isomers), pentyl (various isomers), hexyl (various isomers), heptyl (various isomers), octyl (various isomers), nonyl (various isomers), decyl (various isomers), undecyl (various isomers), dodecyl (various isomers), tridecyl (various isomers), tetradecyl (various isomers), pentadecyl (various isomers), hexadecyl (various isomers), heptadecanyl (various isomers), octadecyl (various isomers), nonadecanyl (various isomers), eicosyl (various isomers), etc.; cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc.; and so on.

[0158] As R 12The aliphatic hydrocarbon group that can contain an oxygen atom can include, for example, methoxymethyl, methoxyethyl (various isomers), methoxypropyl (various isomers), methoxybutyl (various isomers), methoxypentyl (various isomers), methoxyhexyl (various isomers), methoxyheptyl (various isomers), methoxyoctyl (various isomers), methoxynonyl (various isomers), methoxydecyl (various isomers), methoxyundecyl (various isomers), methoxydodecyl (various isomers), methoxytridecyl (various isomers), methoxytetradecyl (various isomers), methoxypentadecanyl (various isomers), methoxyhexadecyl (various isomers), methoxyheptadecyl (various isomers), and methoxyoctadecyl (various isomers). Methoxynonadecanyl (various isomers), ethoxymethyl, ethoxyethyl (various isomers), ethoxypropyl (various isomers), ethoxybutyl (various isomers), ethoxypentyl (various isomers), ethoxyhexyl (various isomers), ethoxyheptyl (various isomers), ethoxyoctyl (various isomers), ethoxynonyl (various isomers), ethoxydecyl (various isomers), ethoxyundecyl (various isomers), ethoxydodecyl (various isomers), ethoxytridecyl (various isomers), ethoxytetradecyl (various isomers), ethoxypentadecanyl (various isomers), ethoxyhexadecyl (various isomers), ethoxyheptadecyl (various isomers), ethoxyoctadecyl (various isomers), propoxymethyl (various isomers) (Icons), propoxyethyl (various isomers), propoxypropyl (various isomers), propoxybutyl (various isomers), propoxypentyl (various isomers), propoxyhexyl (various isomers), propoxyheptyl (various isomers), propoxyoctyl (various isomers), propoxynonyl (various isomers), propoxydecyl (various isomers), propoxyundecyl (various isomers), propoxydodecyl (various isomers), propoxytridecyl (various isomers), propoxytetradecyl (various isomers), propoxypentadecanyl (various isomers), propoxyhexadecyl (various isomers), propoxyheptadecyl (various isomers), butoxymethyl (various isomers), butoxyethyl (various isomers), butoxypropyl (various isomers), butoxy Butyl (various isomers), butoxypentyl (various isomers), butoxyhexyl (various isomers), butoxyheptyl (various isomers), butoxyoctyl (various isomers), butoxynonyl (various isomers), butoxydecyl (various isomers), butoxyundecyl (various isomers), butoxydodecyl (various isomers), butoxytridecyl (various isomers), butoxytetradecyl (various isomers), butoxypentadecanyl (various isomers), butoxyhexadecyl (various isomers), pentoxymethyl (various isomers), pentoxyethyl (various isomers), pentoxypropyl (various isomers), pentoxybutyl (various isomers), pentoxypentyl (various isomers), pentoxyhexyl (various isomers), pentoxyheptyl (various isomers)Pentoxyoctyl (various isomers), Pentoxynonyl (various isomers), Pentoxydecyl (various isomers), Pentoxyundecyl (various isomers), Pentoxydodecyl (various isomers), Pentoxytridecyl (various isomers), Pentoxytetradecyl (various isomers), Pentoxypentadecanyl (various isomers), Hexoxymethyl (various isomers), Hexoxyethyl (various isomers), Hexoxypropyl (various isomers), Hexoxybutyl (various isomers), Hexoxypentyl (various isomers), Hexoxyhexyl (various isomers), Hexoxyheptyl (various isomers), Hexoxyoctyl (various isomers), Hexoxynonyl (various isomers), Hexoxydecyl (various isomers), Hexoxydodecyl (various isomers) (Icons), hexoxytridecyl (various isomers), hexoxytetradecyl (various isomers), heptaoxymethyl (various isomers), heptaoxyethyl (various isomers), heptaoxypropyl (various isomers), heptaoxybutyl (various isomers), heptaoxypentyl (various isomers), heptaoxyhexyl (various isomers), heptaoxyheptyl (various isomers), heptaoxyoctyl (various isomers), heptaoxynonyl (various isomers), heptaoxydecyl (various isomers), heptaoxyundecyl (various isomers), heptaoxydodecyl (various isomers), heptaoxytridecyl (various isomers), octyloxymethyl (various isomers), octyloxyethyl (various isomers), octyloxypropyl (various isomers), octyloxybutyl (various isomers), octyloxypentyl (various isomers) (Icons), octyloxyhexyl (various isomers), octyloxyheptyl (various isomers), octyloxyoctyl (various isomers), octyloxynonyl (various isomers), octyloxydecyl (various isomers), octyloxyundecyl (various isomers), octyloxydodecyl (various isomers), nonoxymethyl (various isomers), nonoxyethyl (various isomers), nonoxypropyl (various isomers), nonoxybutyl (various isomers), nonoxypentyl (various isomers), nonoxyhexyl (various isomers), nonoxyheptyl (various isomers), nonoxyoctyl (various isomers), nonoxynonyl (various isomers), nonoxydecyl (various isomers), nonoxyundecyl (various isomers), decyloxymethyl (various isomers), decyloxyethyl (various isomers) Decoxypropyl (various isomers), Decoxybutyl (various isomers), Decoxypentyl (various isomers), Decoxyhexyl (various isomers), Decoxyheptyl (various isomers), Decoxyoctyl (various isomers), Decoxynonyl (various isomers), Decoxydecyl (various isomers), Undecyloxymethyl (various isomers), Undecyloxyethyl (various isomers), Undecyloxypropyl (various isomers), Undecyloxybutyl (various isomers), Undecyloxypentyl (various isomers), Undecyloxyhexyl (various isomers), Undecyloxyoctyl (various isomers), Undecyloxynonyl (various isomers), Dodecyloxymethyl (various isomers), Dodecyloxyethyl (various isomers)Dodecyloxypropyl (various isomers), dodecyloxybutyl (various isomers), dodecyloxypentyl (various isomers), dodecyloxyhexyl (various isomers), dodecyloxyheptyl (various isomers), tridecyloxymethyl (various isomers), tridecyloxyethyl (various isomers), tridecyloxypropyl (various isomers), tridecyloxybutyl (various isomers), tridecyloxypentyl (various isomers), tridecyloxyhexyl (various isomers), tridecyloxyheptyl (various isomers), tetradecyloxymethyl (various isomers), tetradecyloxyethyl (various isomers), tetradecyloxypropyl (various isomers), tetradecyloxybutyl (...) Alkoxyalkyl groups, including isomers of tetradecyloxypentyl, tetradecyloxyhexyl, pentadecyloxymethyl, pentadecyloxyethyl, pentadecyloxypropyl, pentadecyloxybutyl, pentadecyloxypentyl, hexadecyloxymethyl, hexadecyloxyethyl, hexadecyloxypropyl, hexadecyloxybutyl, heptadecanyloxymethyl, heptadecanyloxyethyl, heptadecanyloxypropyl, octadecyloxymethyl, and octadecyloxyethyl, etc.

[0159] As R 12Aromatic hydrocarbon groups in phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, etc.; methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), methyl Methylpentylphenyl (various isomers), methylhexylphenyl (various isomers), methylheptylphenyl (various isomers), methyloctylphenyl (various isomers), methylnonylphenyl (various isomers), methyldecylphenyl (various isomers), methylundecylphenyl (various isomers), methyldodecylphenyl (various isomers), methyltridecylphenyl (various isomers), diethylphenyl (various isomers), ethylpropylphenyl (various isomers), ethylbutylphenyl (various isomers), ethylpentylphenyl (various isomers), ethylhexylphenyl (various isomers), ethylheptylphenyl (various isomers), ethyloctylphenyl (various isomers), ethylnonylphenyl (various isomers), ethyldecylphenyl (various isomers), ethylundecylphenyl (various isomers) Isomers), ethyl dodecylphenyl (various isomers), dipropylphenyl (various isomers), propyl butylphenyl (various isomers), propyl pentylphenyl (various isomers), propyl hexylphenyl (various isomers), propyl heptylphenyl (various isomers), propyl octylphenyl (various isomers), propyl nonylphenyl (various isomers), propyl decylphenyl (various isomers), propyl undecylphenyl (various isomers), dibutylphenyl (various isomers), butyl pentylphenyl (various isomers), butyl hexylphenyl (various isomers), butyl octylphenyl (various isomers), butyl nonylphenyl (various isomers), butyl decylphenyl (various isomers), dipentylphenyl (various isomers), pentyl hexylphenyl (various isomers) Isomers), pentylheptylphenyl (various isomers), pentyloctylphenyl (various isomers), pentylnonylphenyl (various isomers), dihexylphenyl (various isomers), hexylheptylphenyl (various isomers), hexyloctylphenyl (various isomers), diheptylphenyl (various isomers), trimethylphenyl (various isomers), dimethylethylphenyl (various isomers), dimethylpropylphenyl (various isomers), dimethylbutylphenyl (various isomers), dimethylpentylphenyl (various isomers), dimethylhexylphenyl (various isomers), dimethylheptylphenyl (various isomers), dimethyloctylphenyl (various isomers), dimethylnonylphenyl (various isomers), dimethyldecylphenyl (various isomers), dimethylundecylphenyl (various isomers)Dimethyldodecylphenyl (various isomers), Triethylphenyl (various isomers), Diethylmethylphenyl (various isomers), Diethylpropylphenyl (various isomers), Diethylbutylphenyl (various isomers), Diethylpentylphenyl (various isomers), Diethylhexylphenyl (various isomers), Diethylheptylphenyl (various isomers), Diethyloctylphenyl (various isomers), Diethylnonylphenyl (various isomers), Diethyldecylphenyl (various isomers), Tripropylphenyl (various isomers), Dipropylmethylphenyl (various isomers) Dipropylethylphenyl (various isomers), dipropylbutylphenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), etc.

[0160] As R 12 The aromatic hydrocarbon group that can contain an oxygen atom can include, for example, alkoxyaryl groups such as methoxyphenyl (various isomers) and ethoxyphenyl (various isomers).

[0161] Among them, as R 12Preferred is phenyl, naphthyl, anthracene, pyrene, phenanthrene, methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), methylpentylphenyl (various isomers), methylhexyl Phenyl (various isomers), methyl heptaylphenyl (various isomers), methyl octylphenyl (various isomers), methyl nonylphenyl (various isomers), methyl decylphenyl (various isomers), methyl undecylphenyl (various isomers), methyl dodecylphenyl (various isomers), methyl tridecylphenyl (various isomers), diethylphenyl (various isomers), ethyl propylphenyl (various isomers), ethyl butylphenyl (various isomers), ethyl pentylphenyl (various isomers), ethyl hexylphenyl (various isomers), ethyl heptaylphenyl (various isomers), ethyl octylphenyl (various isomers), ethyl nonylphenyl (various isomers), ethyl decylphenyl (various isomers), ethyl undecylphenyl (various isomers), ethyl dodecylphenyl (various isomers) (Icons), dipropylphenyl (various isomers), propylbutylphenyl (various isomers), propylpentylphenyl (various isomers), propylhexylphenyl (various isomers), propylheptylphenyl (various isomers), propyloctylphenyl (various isomers), propylnonylphenyl (various isomers), propyldecylphenyl (various isomers), propylundecylphenyl (various isomers), dibutylphenyl (various isomers), butylpentylphenyl (various isomers), butylhexylphenyl (various isomers), butylheptylphenyl (various isomers), butyloctylphenyl (various isomers), butylnonylphenyl (various isomers), butyldecylphenyl (various isomers), dipentylphenyl (various isomers), pentylhexylphenyl (various isomers), pentylheptylphenyl (various isomers) ), Pentyloctylphenyl (various isomers), Pentylnonylphenyl (various isomers), Dihexylphenyl (various isomers), Hexylheptylphenyl (various isomers), Hexyloctylphenyl (various isomers), Diheptylphenyl (various isomers), Trimethylphenyl (various isomers), Dimethylethylphenyl (various isomers), Dimethylpropylphenyl (various isomers), Dimethylbutylphenyl (various isomers), Dimethylpentylphenyl (various isomers), Dimethylhexylphenyl (various isomers), Dimethylheptylphenyl (various isomers), Dimethyloctylphenyl (various isomers), Dimethylnonylphenyl (various isomers), Dimethyldecylphenyl (various isomers), Dimethylundecylphenyl (various isomers), Dimethyldodecylphenyl (various isomers)Triethylphenyl (various isomers), diethylmethylphenyl (various isomers), diethylpropylphenyl (various isomers), diethylbutylphenyl (various isomers), diethylpentylphenyl (various isomers), diethylhexylphenyl (various isomers), diethylheptylphenyl (various isomers), diethyloctylphenyl (various isomers), diethylnonylphenyl (various isomers), diethyldecylphenyl (various isomers), tripropylphenyl (various isomers), dipropylmethylphenyl (various isomers), dipropylethylphenyl (various isomers), dipropylbutyl Phenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers). More preferably, phenyl, cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers).

[0162] [n11 and n12]

[0163] n11 is an integer greater than 1 and less than 8.

[0164] n12 represents the number of isocyanate groups, which is an integer between 0 and 7.

[0165] The sum of n11 and n12 (n11+n12) is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4. Generally, the larger the value of (n11+n12), the higher the boiling point becomes as the molecular weight of the carbonyl compound (I) increases, and the easier it is to separate it from the isocyanate. On the other hand, in the manufacture of carbonyl compound (I), if the highly reactive isocyanate group is heated, a modification reaction will occur, which will cause solidification in the device and blockage. From the perspective of the manufacturing efficiency of carbonyl compound (I), it is preferable that (n11+n12) is 6 or less, more preferably (n11+n12) is 5 or less, and even more preferably (n11+n12) is 4 or less.

[0166] Preferred carbonyl compounds (I) include, for example, compounds represented by formulas (I-1a) to (I-24) below (hereinafter sometimes referred to as "carbonyl compound (I-1a)", etc.). It should be noted that carbonyl compounds (I-1a) to (I-1c), carbonyl compounds (I-2a) to (I-2c), carbonyl compounds (I-3a) to (I-3c), carbonyl compounds (I-4a) to (I-4c), carbonyl compounds (I-5a) to (I-5c), carbonyl compounds (I-6a) to (I-6c), carbonyl compounds (I-7a) to (I-7b), and carbonyl compounds (I-8a) to (I-24) are also considered. I-8b), carbonyl compounds (I-9a) to (I-9b), carbonyl compounds (I-10a) to (I-10b), carbonyl compounds (I-11a) to (I-11b), carbonyl compounds (I-12a) to (I-12b), carbonyl compounds (I-22a) to (I-22b), or carbonyl compounds (I-24a) to (I-24b) can be prepared as mixtures or as individual compounds.

[0167] [Chemistry 17]

[0168]

[0169] [Chemistry 18]

[0170]

[0171] [Chemistry 19]

[0172]

[0173] [Chemistry 20]

[0174]

[0175] [Chemistry 21]

[0176]

[0177] [Chemistry 22]

[0178]

[0179] [Chemistry 23]

[0180]

[0181] [Chemistry 24]

[0182]

[0183] Methods for manufacturing carbonyl compounds

[0184] The method for manufacturing the carbonyl compound in this embodiment includes: mixing one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds with...

[0185] Choose one or more compounds from the group consisting of carbonates and hydroxyl compounds.

[0186] The mixture was heated to synthesize the carbonyl compound described above.

[0187] The inventors discovered that the carbonyl compound (I) is generated when isocyanate compounds are produced by the thermal decomposition reaction of urethane compounds.

[0188] Therefore, as a method for manufacturing carbonyl compounds according to this embodiment, the following methods can be cited: 1) a manufacturing method based on the thermal decomposition reaction of urethane compounds; 2) a method of mixing one or more compounds selected from the group consisting of isocyanate compounds and urethane compounds with one or more compounds selected from the group consisting of carbonates and hydroxyl compounds, and then heating the mixture.

[0189] <Manufacturing Method Based on Thermal Decomposition Reaction>

[0190] When carbonyl compounds are produced via thermal decomposition reactions, the following side reactions occur: the formation of isocyanurate groups (represented by formula (B) above), the formation of carbodiimides (represented by formula (C) above), the formation of urea-ketimides (represented by formula (D) above), and the formation of urethane groups (represented by formula (E) above). These side reactions occur through reactions between isocyanates, between carbamate compounds, or between isocyanates and carbamate compounds. In contrast, the formation of carbonyl compound (I) occurs through the reaction of one or more compounds selected from the group consisting of isocyanates and carbamates with one or more compounds selected from the group consisting of carbonates and hydroxyl compounds. Therefore, in the thermal decomposition reaction of carbamate compounds, by increasing the amount of carbonate or by conducting the thermal decomposition reaction under reflux conditions to prevent the evaporation of excess carbonate, the proportion of carbonyl compound (I) formed can be relatively increased.

[0191] Carbonyl compounds (I) are presumed to be generated via the reaction mechanisms represented by the following formulas (F), (G) or (H).

[0192] [Chemistry 25]

[0193]

[0194] (In formulas (F) to (H), R) j It is an organic group with a valence of 2 or higher. R k (It is a monovalent organic group.)

[0195] In the thermal decomposition reaction, from the perspective of suppressing side reactions, it is preferable to use a large amount (molar amount) of carbonate as a solvent. Considering the size of the reactor, the amount is preferably 0.001 times to 100 times, more preferably 0.01 times to 80 times, and even more preferably 0.1 times to 50 times, in terms of the stoichiometric ratio relative to the carbamate compound.

[0196] When manufacturing a carbamate compound by the method described later, if the carbamate compound contains carbonate, the carbonate can be used directly, or a new carbonate can be added to the carbamate compound. Alternatively, the carbonate can be supplied to the reactor before the reaction begins, during the reaction, or both. Preferably, it is supplied to the reactor before the reaction.

[0197] The reaction temperature is typically between 100°C and 400°C. Higher temperatures are preferred to increase the reaction rate. However, at high temperatures, the aforementioned side reactions may occur due to one or more compounds selected from the group consisting of urethane compounds and isocyanate compounds as products. Therefore, the reaction temperature is preferably between 130°C and 300°C, more preferably between 150°C and 280°C. To maintain a constant reaction temperature, known cooling or heating devices can be installed in the reactor.

[0198] Furthermore, the reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or increased pressure, typically above 20 Pa (1×10⁻⁶). 6 The range is below Pa.

[0199] There are no particular restrictions on the reaction time (retention time in the case of continuous methods), which is usually 0.001 hours to 100 hours, preferably 0.01 hours to 50 hours, and more preferably 0.1 hours to 10 hours.

[0200] A catalyst may be used, and the amount of catalyst used relative to the mass of the carbamate compound is preferably 0.01% to 30% by mass, more preferably 0.5% to 20% by mass.

[0201] Examples of organometallic catalysts include dibutyltin dilaurate, lead octanoate, and stannous octanoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine, and triethylamine. Among these, dibutyltin dilaurate, lead octanoate, and stannous octanoate are particularly suitable. These compounds can be used alone or in mixtures of two or more.

[0202] As described above, the thermal decomposition reaction is a reaction in which a urethane compound is converted into a corresponding isocyanate compound, a hydroxyl compound, and a carbonyl compound. To efficiently obtain the carbonyl compound, heating is required in the thermal decomposition reaction in a state where the isocyanate compound, carbonate, and urethane compound coexist. Therefore, in order to efficiently obtain the carbonyl compound in the thermal decomposition reaction, it is preferable to remove the hydroxyl compound, which is a product of the thermal decomposition reaction, from the thermal decomposition reaction system as a gaseous component by methods such as distillation, and then separate the hydroxyl compound from the carbonate and isocyanate compound under reflux or similar conditions, so that the carbonate and the isocyanate exist as liquid components.

[0203] After the thermal decomposition reaction, light boiling components can be removed by distillation. There are no particular limitations on the distillation method as long as the light boiling components can be separated in the form of gaseous components. The term "light boiling components" here refers to components with boiling points lower than those of carbonyl compounds. Although this varies depending on the type of compound used as a raw material for manufacturing the carbonyl compound, these light boiling components are primarily one or more compounds selected from the group consisting of carbonates used in the thermal decomposition process, isocyanate compounds generated in the thermal decomposition reaction, and hydroxyl compounds.

[0204] The pressure used for distillation to remove light boiling components varies depending on the type of compound and the reaction temperature. Within the range sufficient to separate carbonyl compounds from light boiling components, it can be any of reduced pressure, atmospheric pressure, or pressurized pressure, preferably 20 Pa or higher (1 × 10⁻⁶). 6 Pa or less, more preferably 20 Pa or more, 1×10 4 Pa below, more preferably above 20 Pa, 1×10 3 Below 20 Pa, especially preferably above 20 Pa, 1×10 2 Below Pa.

[0205] Regarding the operation time (retention time in the case of continuous methods) for removing light boiling components by distillation, there is no particular limitation within the range that allows for the separation of carbonyl compounds and light boiling components. From the perspective of suppressing side reactions with carbonyl compounds, it is preferably 5 seconds to 100 hours, more preferably 10 seconds to 50 hours, and even more preferably 20 seconds to 10 hours.

[0206] Regarding the temperature for distilling to remove light boiling components, there are no particular limitations within a range that allows the carbonyl compound to be stable and separate from the light boiling components. From the perspective of suppressing the modification of the carbonyl compound, it is preferably 20°C to 300°C, more preferably 30°C to 280°C, and even more preferably 40°C to 250°C.

[0207] <Manufacturing Method Based on Heating of Mixtures>

[0208] As can be seen from the reaction mechanism of carbonyl compounds represented by the above formulas (F), (G) or (H), carbonyl compound (I) can also be obtained by heating a mixture of isocyanate compound (II) and carbonate (IV), a mixture of urethane compound (III) or urethane compound (VI) and carbonate (IV), a mixture of isocyanate compound (II) and hydroxy compound (V) and carbonate (IV), a mixture of isocyanate compound (II) and urethane compound (III) or urethane compound (VI) and carbonate (IV), or a mixture of isocyanate compound (II) and urethane compound (III) or urethane compound (VI) and carbonate (IV) and hydroxy compound (V) (hereinafter, these mixtures are sometimes referred to together as "starter mixtures").

[0209] In the raw material mixture, from the perspective of suppressing side reactions, it is preferable to have a large amount (molar amount) of carbonate. Considering the size of the reactor, etc., it is preferably 0.001 times to 100 times, more preferably 0.01 times to 80 times, and even more preferably 0.1 times to 50 times, in terms of the stoichiometric ratio relative to the carbamate compound.

[0210] The heating temperature is typically between 100°C and 400°C. Higher temperatures are preferred to increase the reaction rate. However, at high temperatures, the aforementioned side reactions may occur due to one or more compounds selected from the group consisting of urethane compounds and isocyanate compounds as products. Therefore, temperatures between 130°C and 300°C, and more preferably between 150°C and 280°C, are preferred. To maintain a constant reaction temperature, known cooling and heating devices can be installed in the reactor.

[0211] The heating pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or increased pressure, typically above 20 Pa (1×10⁻⁶). 6 The range is below Pa.

[0212] There are no particular restrictions on the heating time (or residence time in the case of continuous methods), which is usually 0.001 hours to 100 hours, preferably 0.01 hours to 50 hours, and more preferably 0.1 hours to 10 hours.

[0213] In the production of carbonyl compounds based on mixed heating, the formation rate and quantity of carbonyl compounds can be increased by contacting a mixture of raw materials with a stainless steel liquid and then heating it. The stainless steel can be either SUS316 or SUS304, regardless of its shape; for example, fillers or metal sheets are preferred. There are no particular limitations on the filler material; DIXON packing, McMAHON packing, Coil pack, MESH ring, CANNON packing, HELIPACK, RASCHIG ring, PRICKLE ring, etc., can be used.

[0214] When setting the volume V of the carbonyl compound feed solution and the surface area A of the stainless steel, the larger the contact area between the feed solution per unit volume and the stainless steel, the faster the carbonyl compound is formed. The preferred value for A / V is 0.001 m. 2 / m 3 The above 100,000m 2 / m 3 The following, or more preferably, is 0.01m 2 / m 3 Above 50,000m 2 / m 3 The following, and more preferably, is 0.1m 2 / m 3 Above 10000m 2 / m 3 the following.

[0215] The reaction method is not particularly limited, but a reactor that can effectively mix and heat the raw material mixture or the mixture with stainless steel is preferred. For example, a method of heating the raw material mixture using a stirred tank or distillation column made of stainless steel is preferred.

[0216] Lightly boiling components can be removed by distillation after heating the raw material mixture. There are no particular limitations on the distillation method as long as the lightly boiling components can be separated in the form of gaseous components. The term "lightly boiling components (lightly boiling point components)" refers to components with boiling points lower than those of carbonyl compounds. Although this varies depending on the type of compound used as a raw material for manufacturing carbonyl compounds, these lightly boiling components are primarily selected from one or more compounds in the group consisting of carbonates contained in the raw material mixture, isocyanate compounds generated in thermal decomposition reactions, and hydroxyl compounds.

[0217] The pressure used for distillation to remove light boiling components varies depending on the type of compound and the reaction temperature. Within the range sufficient to separate carbonyl compounds from light boiling components, it can be any of reduced pressure, atmospheric pressure, or pressurized pressure, preferably 20 Pa or higher (1 × 10⁻⁶). 6 Pa or less, more preferably 20 Pa or more, 1×104 Pa below, more preferably above 20 Pa, 1×10 3 Below 20 Pa, especially preferably above 20 Pa, 1×10 2 Below Pa.

[0218] Regarding the operation time (retention time in the case of continuous methods) for removing light boiling components by distillation, there is no particular limitation within the range that allows for the separation of carbonyl compounds and light boiling components. From the perspective of suppressing side reactions with carbonyl compounds, it is preferably 5 seconds to 100 hours, more preferably 10 seconds to 50 hours, and even more preferably 20 seconds to 10 hours.

[0219] Regarding the temperature for distilling to remove light boiling components, there are no particular limitations within a range that allows the carbonyl compound to be stable and separate from the light boiling components. From the perspective of suppressing the modification of the carbonyl compound, it is preferably 20°C to 300°C, more preferably 30°C to 280°C, and even more preferably 40°C to 250°C.

[0220] Next, the various raw materials used in the method for manufacturing the carbonyl compound of this embodiment will be described in detail below.

[0221] <Isocyanate compounds>

[0222] As isocyanate compounds, compounds represented by the following general formula (II) are preferred (hereafter referred to as "isocyanate compound (II)").

[0223] [Chemistry 26]

[0224]

[0225] (In general formula (II), R) 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 (where n21 is an integer greater than 2 and less than 8, satisfying the relation: n21 = n11 + n12.)

[0226] [R 21 ]

[0227] R 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 That is, R 21 With the above R 11 same.

[0228] R 21In the case of an aliphatic hydrocarbon group, as an isocyanate compound (II), specifically, examples include aliphatic diisocyanates, aliphatic triisocyanates, substituted cyclic aliphatic polyisocyanates, etc.

[0229] Examples of aliphatic diisocyanates include diisocyanate ethane, diisocyanate propane (various isomers), diisocyanate butane (various isomers), diisocyanate pentane (various isomers), diisocyanate hexane (various isomers), and diisocyanate decane (various isomers).

[0230] Examples of aliphatic triisocyanates include triisocyanate hexane (various isomers), 4-isocyanate methyl-1,8-octamethylene diisocyanate, triisocyanate nonane (various isomers), and triisocyanate decane (various isomers).

[0231] Examples of substituted cyclic aliphatic polyisocyanates include diisocyanate cyclobutane (various isomers), diisocyanate cyclohexane (various isomers), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (also known as isophorone diisocyanate) (various isomers), 1,3-bis(isocyanate methyl)cyclohexane (at least one of the cis and trans isomers), and methylene bis(cyclohexyl isocyanate) (also known as dicyclohexylmethane diisocyanate) (various isomers).

[0232] R 21 In the case of an aromatic group, as an isocyanate compound (II), specifically, for example, aromatic diisocyanates, aromatic triisocyanates, etc.

[0233] Examples of aromatic diisocyanates include diisocyanate phenyl (various isomers), diisocyanate toluene (various isomers), bis(isocyanate phenyl)methane (various isomers), diisocyanate tricene (various isomers), diisocyanate biphenyl (various isomers), diisocyanate bibenzyl (various isomers), bis(isocyanate phenyl)propane (various isomers), bis(isocyanate phenyl)ether (various isomers), and bis(isocyanate phenoxy) Ethane (various isomers), xylene diisocyanate (various isomers), anisole diisocyanate (various isomers), phenethyl diisocyanate (various isomers), naphthalene diisocyanate (various isomers), methylbenzene diisocyanate (various isomers), methylpyridine diisocyanate (various isomers), methylnaphthalene diisocyanate (various isomers), diphenylmethane diisocyanate (various isomers), tetramethylphenyl dimethyl diisocyanate (various isomers), etc.

[0234] Examples of aromatic triisocyanates include triisocyanate phenyl (various isomers), triisocyanate-methylbenzene (various isomers), tri(isocyanate-propane-yl)benzene (various isomers), tri(isocyanate-propane-yl)-methylbenzene (various isomers), tri(isocyanate-methyl)-methylbenzene (various isomers), and ((isocyanate-phenylene)bis(methylene))bis(isocyanate-phenylene) (various isomers).

[0235] R 21 In the case of aromatic compounds, the reactivity of directly bonded isocyanate groups increases due to the electron-withdrawing effect of aromatic groups. Furthermore, as the number of isocyanate groups directly bonded to the same aromatic compound increases, reactivity further increases due to mutual electron-withdrawing interactions. From a reactivity perspective, relative to R... 21 The isocyanate group preferably has 2 or more, more preferably 3 or more. On the other hand, if the reactivity of the isocyanate increases, reactions may occur between water or between isocyanates, as well as with other impurities, reducing the stability of the compound at room temperature and under heating. From the perspective of the stability of the isocyanate compound, with R... 21 The number of directly bonded isocyanate groups is preferably 4 or less, more preferably 3 or less.

[0236] R 21When the aliphatic hydrocarbon group or aromatic group in the compound has one or more but four ester groups or nitrogen atoms, it is an isocyanate compound (II). Specifically, examples include, for instance, ethyl 2-isocyanate, ethyl 2-methacrylate, propyl 2-isocyanate, propyl 2-methacrylate, propyl 3-isocyanate, and propyl 2-methyl- 3-Isocyanate-propyl acrylate, 4-Isocyanate-butyl acrylate, 2-Methacryl-4-isocyanate-butyl acrylate, 5-Isocyanate-pentyl acrylate, 2-Methacryl-5-isocyanate-pentyl acrylate, 6-Isocyanate-hexyl acrylate, 2-Methacryl-6-isocyanate-hexyl acrylate, 8-Isocyanate-octyl acrylate, 2-Methacryl-8-isocyanate -Octyl acrylate, 10-Isocyanate-decyl acrylate, 2-Methyl-10-Isocyanate-decyl acrylate, 11-Isocyanate-undecyl acrylate, 2-Methyl-11-Isocyanate-undecyl acrylate, 12-Isocyanate-dodecyl acrylate, 2-Methyl-12-Isocyanate-dodecyl acrylate, Lysine methyl ester diisocyanate, Lysine ethyl ester diisocyanate, 2- Ethyl isocyanate-2,5-diisocyanate-valerate, 2-ethyl isocyanate-2,6-diisocyanate-hexanoate (lysine triisocyanate), bis(2-ethyl isocyanate)-2-isocyanate-succinate, bis(2-ethyl isocyanate)-2-isocyanate-glutarate, tris(2-ethyl isocyanate)hexane-1,3,6-tricarboxylate, triisocyanate-ethylamine, triisocyanate-propylamine, etc.

[0237] By incorporating electron-withdrawing groups such as ester groups and nitrogen atoms into isocyanate compounds, the reactivity of the isocyanate group is enhanced. The fewer the number of carbon atoms between the isocyanate group and the ester group or nitrogen atom, the higher the reactivity of the isocyanate group. Therefore, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 8, and even more preferably 1 to 3. On the other hand, the carbon-carbon or carbon-nitrogen bond between the isocyanate group (as an electron-withdrawing group) and the ester group or nitrogen atom is easily dissociated, potentially impairing the thermal stability of the compound. Therefore, from the perspective of the stability of compounds in which isocyanate groups coexist with ester groups or nitrogen atoms, the more carbon atoms between the isocyanate group and the ester group or nitrogen atom, the higher the stability of the compound. Therefore, the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.

[0238] Isocyanate compounds (II) are mostly used as raw materials for coatings, requiring them to have the property of not discoloring when exposed to sunlight or other light (weather resistance). If R 21Products containing aromatic groups will undergo coloration upon exposure to sunlight due to the absorption of light energy. Therefore, from a weather resistance perspective, R is preferred. 21 It does not have an aromatic group, and is more preferably an aliphatic hydrocarbon group with a carbon number of 1 to 20 and a valence of 1 to 4 or more ester groups or nitrogen atoms, which may have a divalent to a tetravalent group.

[0239] Additionally, as R 21 Specifically, it is preferred to be a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formulas (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18) or (Ia-19).

[0240] (n21)

[0241] n21 represents the number of isocyanate groups, satisfying the relationship: n21 = n11 + n12. n21 is an integer of 2 to 8, preferably 2 to 6, more preferably 2 to 5, and even more preferably 3 to 4. Generally, polymers are obtained by reacting isocyanates with an isocyanate valence of n21 or higher with a dihydroxy compound or diamine compound having an active hydrogen group. The larger the value of n21, the more crosslinking points (isocyanate groups) there are per isocyanate molecule, thus increasing the crosslinking density during polymer production, which shortens curing time and improves polymer hardness. It should be noted that "increased crosslinking density" here refers to a decrease in the average molecular chain length between crosslinking points. If the isocyanate molecule has 3 or more isocyanate groups (n21 is 3 or more), it allows for further bonding between linear polymer chains, easily increasing the polymer's molecular weight. Therefore, it is particularly expected to significantly shorten curing time and significantly improve polymer properties such as hardness. On the other hand, if a highly reactive isocyanate compound is heated during the manufacture of isocyanate, a modification reaction will occur, which will cause it to solidify in the device and cause blockage. Therefore, the valence n21 of the isocyanate group in the isocyanate compound is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less.

[0242] Preferred isocyanate compounds (II) include, for example, 4-isocyanate methyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanate ethyl-2,6-diisocyanate hexanoate (LTI), lysine methyl ester diisocyanate (LDI), methylene bis(cyclohexyl isocyanate) (HMDI), 1,3-bis(isocyanate methyl)cyclohexane (HXDI), and diisocyanate diphenylmethane (MDI).

[0243] <Carbamate Compounds>

[0244] As a carbamate compound, it is preferred to use a compound represented by the following general formula (III) (hereinafter sometimes referred to as "carbamate compound (III)") or a compound represented by the following general formula (VI) (hereinafter sometimes referred to as "carbamate compound (VI)").

[0245] [Chemistry 27]

[0246]

[0247] (In general formula (III), R) 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 Let n31 be an integer greater than or equal to 1 and less than or equal to 8, and n32 be an integer greater than or equal to 0 and less than or equal to 7. The sum of n31 and n32 is an integer greater than or equal to 2 and less than or equal to 8, satisfying the relation: n31 + n32 = n11 + n12.

[0248] [Chemistry 28]

[0249]

[0250] (In general formula (VI), R) 61 For organic groups with an n61 valence, the following relationship is satisfied: R 61 =R 21 R 62 For a monovalent organic group, the following relationship is satisfied: R 62 =R 12 (where n61 is an integer greater than 2 and less than 8, satisfying the relation: n61 = n21.)

[0251] [Carbamate Compound (III)]

[0252] (R 31 )

[0253] R 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 That is, R 31 With the above R 11 same.

[0254] Among them, as R 31 Preferably, it can have one or more ester groups or less than four nitrogen atoms, and be aliphatic hydrocarbon groups with a carbon number of 1 or more than 20 and a valence of 2 to 4 or a valence of 6 to 20 or a valence of 2 to 3 or a valence of 3.

[0255] Additionally, as R 31 Specifically, it is preferred to be a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formulas (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18) or (Ia-19).

[0256] (R 32 )

[0257] R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 That is, R 32 With the above R 12 same.

[0258] Among them, as R 32 Preferably, it can contain an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0259] Additionally, as R 32Specifically, the preferred isomeric compounds are phenyl, naphthyl, anthraceneyl, pyrene, phenanthrene, methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), and methylpentylphenyl (various isomers). Methylhexylphenyl (various isomers), methylheptylphenyl (various isomers), methyloctylphenyl (various isomers), methylnonylphenyl (various isomers), methyldecylphenyl (various isomers), methylundecylphenyl (various isomers), methyldodecylphenyl (various isomers), methyltridecylphenyl (various isomers), diethylphenyl (various isomers), ethylpropylphenyl (various isomers), ethylbutylphenyl (various isomers), ethylpentylphenyl (various isomers), ethylhexylphenyl (various isomers), ethylheptylphenyl (various isomers), ethyloctylphenyl (various isomers), ethylnonylphenyl (various isomers), ethyldecylphenyl (various isomers), ethylundecylphenyl (various isomers), ethyldodecylphenyl (Isomers), dipropylphenyl (isomers), propylbutylphenyl (isomers), propylpentylphenyl (isomers), propylhexylphenyl (isomers), propylheptylphenyl (isomers), propyloctylphenyl (isomers), propylnonylphenyl (isomers), propyldecylphenyl (isomers), propylundecylphenyl (isomers), dibutylphenyl (isomers), butylpentylphenyl (isomers), butylhexylphenyl (isomers), butylheptylphenyl (isomers), butyloctylphenyl (isomers), butylnonylphenyl (isomers), butyldecylphenyl (isomers), dipentylphenyl (isomers), pentylhexylphenyl (isomers), pentylheptylphenyl (isomers) (Icons), pentyl octylphenyl (various isomers), pentyl nonylphenyl (various isomers), dihexylphenyl (various isomers), hexyl heptylphenyl (various isomers), hexyl octylphenyl (various isomers), diheptylphenyl (various isomers), trimethylphenyl (various isomers), dimethyl ethylphenyl (various isomers), dimethyl propylphenyl (various isomers), dimethyl butylphenyl (various isomers), dimethyl pentylphenyl (various isomers), dimethyl hexylphenyl (various isomers), dimethyl heptylphenyl (various isomers), dimethyl octylphenyl (various isomers), dimethyl nonylphenyl (various isomers), dimethyl decylphenyl (various isomers), dimethyl undecylphenyl (various isomers), dimethyl dodecylphenyl (various isomers)Triethylphenyl (various isomers), diethylmethylphenyl (various isomers), diethylpropylphenyl (various isomers), diethylbutylphenyl (various isomers), diethylpentylphenyl (various isomers), diethylhexylphenyl (various isomers), diethylheptylphenyl (various isomers), diethyloctylphenyl (various isomers), diethylnonylphenyl (various isomers), diethyldecylphenyl (various isomers), tripropylphenyl (various isomers), dipropylmethylphenyl (various isomers), dipropylethylphenyl (various isomers), dipropylbutyl Dipropylphenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers). More preferably, phenyl, cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers).

[0260] (n31 and n32)

[0261] n31 is an integer greater than 1 and less than 8.

[0262] n32 is an integer greater than 0 and less than 7.

[0263] The sum of n31 and n32 is an integer greater than 2 and less than 8, satisfying the relation: n31 + n32 = n11 + n12.

[0264] Preferred carbamate compounds (III) include, for example, compounds represented by the formulas (III-1a) to (III-24b). It should be noted that carbamate compounds (III-1a) to (III-1c), carbamate compounds (III-2a) to (III-2c), carbamate compounds (III-3a) to (III-3c), carbamate compounds (III-4a) to (III-4c), carbamate compounds (III-5a) to (III-5c), carbamate compounds (III-6a) to (III-6c), carbamate compounds (III-7a) to (III-7b), and carbamate compounds (III- 8a)~(III-8b), carbamate compounds (III-9a)~(III-9b), carbamate compounds (III-10a)~(III-10b), carbamate compounds (III-11a)~(III-11b), carbamate compounds (III-12a)~(III-12b), carbamate compounds (III-22a)~(III-22b), or carbamate compounds (III-24a)~(III-24b) can be prepared as mixtures or as individual compounds.

[0265] [Chemistry 29]

[0266]

[0267] [Chemistry 30]

[0268]

[0269] [Chemistry 31]

[0270]

[0271] [Chemistry 32]

[0272]

[0273] [Chemistry 33]

[0274]

[0275] [Chemistry 34]

[0276]

[0277] [Chemistry 35]

[0278]

[0279] [Chemistry 36]

[0280]

[0281] [Carbamate compound (VI)]

[0282] (R 61 )

[0283] R 61 For organic groups with an n61 valence, the following relationship is satisfied: R 61 =R 21 That is, R 61 With the above R 21 same.

[0284] Among them, as R 61 Preferably, it can be an aliphatic hydrocarbon group with 1 to 4 ester groups or nitrogen atoms and 1 to 20 carbon atoms, having a valence of 2 to 4 or a valence of 6 to 20 or a valence of 2 to 3 or a valence of 3.

[0285] Additionally, as R 61 Specifically, it is preferred to be a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formulas (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18) or (Ia-19).

[0286] (R 62 )

[0287] R 62 For a monovalent organic group, the following relationship is satisfied: R 62 =R 12 That is, R 62 With the above R 12 same.

[0288] Among them, as R 62 Preferably, it can contain an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0289] Additionally, as R 62Specifically, the preferred isomeric compounds are phenyl, naphthyl, anthraceneyl, pyrene, phenanthrene, methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), and methylpentylphenyl (various isomers). Methylhexylphenyl (various isomers), methylheptylphenyl (various isomers), methyloctylphenyl (various isomers), methylnonylphenyl (various isomers), methyldecylphenyl (various isomers), methylundecylphenyl (various isomers), methyldodecylphenyl (various isomers), methyltridecylphenyl (various isomers), diethylphenyl (various isomers), ethylpropylphenyl (various isomers), ethylbutylphenyl (various isomers), ethylpentylphenyl (various isomers), ethylhexylphenyl (various isomers), ethylheptylphenyl (various isomers), ethyloctylphenyl (various isomers), ethylnonylphenyl (various isomers), ethyldecylphenyl (various isomers), ethylundecylphenyl (various isomers), ethyldodecylphenyl (Isomers), dipropylphenyl (isomers), propylbutylphenyl (isomers), propylpentylphenyl (isomers), propylhexylphenyl (isomers), propylheptylphenyl (isomers), propyloctylphenyl (isomers), propylnonylphenyl (isomers), propyldecylphenyl (isomers), propylundecylphenyl (isomers), dibutylphenyl (isomers), butylpentylphenyl (isomers), butylhexylphenyl (isomers), butylheptylphenyl (isomers), butyloctylphenyl (isomers), butylnonylphenyl (isomers), butyldecylphenyl (isomers), dipentylphenyl (isomers), pentylhexylphenyl (isomers), pentylheptylphenyl (isomers) (Icons), pentyl octylphenyl (various isomers), pentyl nonylphenyl (various isomers), dihexylphenyl (various isomers), hexyl heptylphenyl (various isomers), hexyl octylphenyl (various isomers), diheptylphenyl (various isomers), trimethylphenyl (various isomers), dimethyl ethylphenyl (various isomers), dimethyl propylphenyl (various isomers), dimethyl butylphenyl (various isomers), dimethyl pentylphenyl (various isomers), dimethyl hexylphenyl (various isomers), dimethyl heptylphenyl (various isomers), dimethyl octylphenyl (various isomers), dimethyl nonylphenyl (various isomers), dimethyl decylphenyl (various isomers), dimethyl undecylphenyl (various isomers), dimethyl dodecylphenyl (various isomers)Triethylphenyl (various isomers), diethylmethylphenyl (various isomers), diethylpropylphenyl (various isomers), diethylbutylphenyl (various isomers), diethylpentylphenyl (various isomers), diethylhexylphenyl (various isomers), diethylheptylphenyl (various isomers), diethyloctylphenyl (various isomers), diethylnonylphenyl (various isomers), diethyldecylphenyl (various isomers), tripropylphenyl (various isomers), dipropylmethylphenyl (various isomers), dipropylethylphenyl (various isomers), dipropylbutyl Dipropylphenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers). More preferably, phenyl, cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers).

[0290] (n61)

[0291] n61 represents the number of urethane groups, satisfying the relationship: n61 = n21. n61 is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4.

[0292] Preferred carbamate compounds (VI) include, for example, compounds represented by the following formulas (VI-1) to (VI-24).

[0293] [Chemistry 37]

[0294]

[0295] [Chemistry 38]

[0296]

[0297] [Chemistry 39]

[0298]

[0299] <carbonate>

[0300] As a carbonate, compounds represented by the following general formula (IV) are preferred (hereafter referred to as "carbonate (IV)").

[0301] [Chemistry 40]

[0302]

[0303] (In general formula (IV), R) 41 and R 42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 。 )

[0304] [R 41 and R 42 ]

[0305] R 41 and R 42 They are identical and satisfy the relation: R 41 =R 42 =R 12 That is, as R 41 and R 42 Examples of R mentioned above can be cited. 12 The same group is shown in the example.

[0306] Among them, as R 41 and R 42 Preferably, substituted or unsubstituted aryl groups are used.

[0307] Furthermore, more preferred are phenyl, naphthyl, anthraceneyl, pyrene, phenanthryl, methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), methylpentylphenyl (various isomers), and so on. Methylhexylphenyl (various isomers), methylheptylphenyl (various isomers), methyl octylphenyl (various isomers), methyl nonylphenyl (various isomers), methyl decylphenyl (various isomers), methyl undecylphenyl (various isomers), methyl dodecylphenyl (various isomers), methyl tridecylphenyl (various isomers), diethylphenyl (various isomers), ethylpropylphenyl (various isomers), ethyl butylphenyl (various isomers), ethyl pentylphenyl (various isomers), ethyl hexylphenyl (various isomers), ethyl heptaylphenyl (various isomers), ethyl octylphenyl (various isomers), ethyl nonylphenyl (various isomers), ethyl decylphenyl (various isomers), ethyl undecylphenyl (various isomers), ethyl dodecylphenyl ( (Isomers), dipropylphenyl (isomers), propylbutylphenyl (isomers), propylpentylphenyl (isomers), propylhexylphenyl (isomers), propylheptylphenyl (isomers), propyloctylphenyl (isomers), propylnonylphenyl (isomers), propyldecylphenyl (isomers), propylundecylphenyl (isomers), dibutylphenyl (isomers), butylpentylphenyl (isomers), butylhexylphenyl (isomers), butylheptylphenyl (isomers), butyloctylphenyl (isomers), butylnonylphenyl (isomers), butyldecylphenyl (isomers), dipentylphenyl (isomers), pentylhexylphenyl (isomers), pentylheptylphenyl (isomers) (Isomeric), pentyl octylphenyl (various isomers), pentyl nonylphenyl (various isomers), dihexylphenyl (various isomers), hexyl heptylphenyl (various isomers), hexyl octylphenyl (various isomers), diheptylphenyl (various isomers), trimethylphenyl (various isomers), dimethyl ethylphenyl (various isomers), dimethyl propylphenyl (various isomers), dimethyl butylphenyl (various isomers), dimethyl pentylphenyl (various isomers), dimethyl hexylphenyl (various isomers), dimethyl heptylphenyl (various isomers), dimethyl octylphenyl (various isomers), dimethyl nonylphenyl (various isomers), dimethyl decylphenyl (various isomers), dimethyl undecylphenyl (various isomers), dimethyl dodecylphenyl (various isomers)Triethylphenyl (various isomers), diethylmethylphenyl (various isomers), diethylpropylphenyl (various isomers), diethylbutylphenyl (various isomers), diethylpentylphenyl (various isomers), diethylhexylphenyl (various isomers), diethylheptylphenyl (various isomers), diethyloctylphenyl (various isomers), diethylnonylphenyl (various isomers), diethyldecylphenyl (various isomers), tripropylphenyl (various isomers), dipropylmethylphenyl (various isomers), dipropylethylphenyl (various isomers), dipropylbutyl Dipropylphenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers).

[0308] Furthermore, phenyl, methoxyphenyl (each isomer) or ethoxyphenyl (each isomer) are preferred.

[0309] Preferred carbonates (IV) include, for example, diphenyl carbonate, bis(4-cumylphenyl) carbonate, bis(2-methoxyphenyl) carbonate, and bis(2-ethoxyphenyl) carbonate.

[0310] Hydroxy compounds

[0311] As a hydroxyl compound, it is preferred to use a compound represented by the following general formula (V) (hereinafter sometimes referred to as "hydroxyl compound (V)").

[0312] [Chemistry 41]

[0313] R 51 -OH (V)

[0314] (In general formula (V), R) 51 For a monovalent organic group, the following relationship is satisfied: R 51 =R 12 。 )

[0315] [R 51 ]

[0316] R 51 For a monovalent organic group, the following relationship is satisfied: R 51 =R 12 That is, R 51 With the above R 12 same.

[0317] Among them, as R51 Preferably, it can contain an aliphatic hydrocarbon group with 1 to 20 carbon atoms or an aromatic hydrocarbon group with 6 to 20 carbon atoms.

[0318] Additionally, as R 51Specifically, the preferred isomeric compounds are phenyl, naphthyl, anthraceneyl, pyrene, phenanthrene, methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), undecylphenyl (various isomers), dodecylphenyl (various isomers), tridecylphenyl (various isomers), tetradecylphenyl (various isomers), dimethylphenyl (various isomers), methylethylphenyl (various isomers), methylpropylphenyl (various isomers), methylbutylphenyl (various isomers), and methylpentylphenyl (various isomers). Methylhexylphenyl (various isomers), methylheptylphenyl (various isomers), methyloctylphenyl (various isomers), methylnonylphenyl (various isomers), methyldecylphenyl (various isomers), methylundecylphenyl (various isomers), methyldodecylphenyl (various isomers), methyltridecylphenyl (various isomers), diethylphenyl (various isomers), ethylpropylphenyl (various isomers), ethylbutylphenyl (various isomers), ethylpentylphenyl (various isomers), ethylhexylphenyl (various isomers), ethylheptylphenyl (various isomers), ethyloctylphenyl (various isomers), ethylnonylphenyl (various isomers), ethyldecylphenyl (various isomers), ethylundecylphenyl (various isomers), ethyldodecylphenyl (Isomers), dipropylphenyl (isomers), propylbutylphenyl (isomers), propylpentylphenyl (isomers), propylhexylphenyl (isomers), propylheptylphenyl (isomers), propyloctylphenyl (isomers), propylnonylphenyl (isomers), propyldecylphenyl (isomers), propylundecylphenyl (isomers), dibutylphenyl (isomers), butylpentylphenyl (isomers), butylhexylphenyl (isomers), butylheptylphenyl (isomers), butyloctylphenyl (isomers), butylnonylphenyl (isomers), butyldecylphenyl (isomers), dipentylphenyl (isomers), pentylhexylphenyl (isomers), pentylheptylphenyl (isomers) (Icons), pentyl octylphenyl (various isomers), pentyl nonylphenyl (various isomers), dihexylphenyl (various isomers), hexyl heptylphenyl (various isomers), hexyl octylphenyl (various isomers), diheptylphenyl (various isomers), trimethylphenyl (various isomers), dimethyl ethylphenyl (various isomers), dimethyl propylphenyl (various isomers), dimethyl butylphenyl (various isomers), dimethyl pentylphenyl (various isomers), dimethyl hexylphenyl (various isomers), dimethyl heptylphenyl (various isomers), dimethyl octylphenyl (various isomers), dimethyl nonylphenyl (various isomers), dimethyl decylphenyl (various isomers), dimethyl undecylphenyl (various isomers), dimethyl dodecylphenyl (various isomers)Triethylphenyl (various isomers), diethylmethylphenyl (various isomers), diethylpropylphenyl (various isomers), diethylbutylphenyl (various isomers), diethylpentylphenyl (various isomers), diethylhexylphenyl (various isomers), diethylheptylphenyl (various isomers), diethyloctylphenyl (various isomers), diethylnonylphenyl (various isomers), diethyldecylphenyl (various isomers), tripropylphenyl (various isomers), dipropylmethylphenyl (various isomers), dipropylethylphenyl (various isomers), dipropylbutyl Dipropylphenyl (various isomers), dipropylpentylphenyl (various isomers), dipropylhexylphenyl (various isomers), dipropylheptylphenyl (various isomers), dipropyloctylphenyl (various isomers), tributylphenyl (various isomers), dibutylmethylphenyl (various isomers), dibutylethylphenyl (various isomers), dibutylpropylphenyl (various isomers), dibutylpentylphenyl (various isomers), dibutylhexylphenyl (various isomers), cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers). More preferably, phenyl, cumylphenyl (various isomers), methoxyphenyl (various isomers), or ethoxyphenyl (various isomers).

[0319] Preferred hydroxyl compounds (V) include aromatic hydroxyl compounds represented by the following general formula (V-1) (hereinafter sometimes referred to as "aromatic hydroxyl compounds (V-1)").

[0320] [Chemistry 42]

[0321]

[0322] (In general formula (V-1), ring A) 511 It is an aromatic hydrocarbon ring with 6 to 20 carbon atoms. 511 It can be a hydrogen atom, an alkyl group with 1 to 20 carbon atoms, an alkoxy group with 1 to 20 carbon atoms, an aryl group with 6 to 20 carbon atoms, an aryloxy group with 6 to 20 carbon atoms, an aralkyl group with 7 to 20 carbon atoms, an aralkyloxy group with 7 to 20 carbon atoms, or a hydroxyl group. 511 Can be used with ring A 511 They bond together to form a ring structure. Additionally, n511 is an integer greater than 1 and less than 10.

[0323] [R 511 ]

[0324] As R 511Alkyl groups with 1 to 20 carbon atoms include, for example, methyl, ethyl, propyl (various isomers), butyl (various isomers), pentyl (various isomers), hexyl (various isomers), heptyl (various isomers), octyl (various isomers), nonyl (various isomers), decyl (various isomers), dodecyl (various isomers), octadecyl (various isomers), etc.

[0325] As R 511 Alkoxy groups with 1 to 20 carbon atoms include, for example, methoxy, ethoxy, propoxy (various isomers), butoxy (various isomers), pentoxy (various isomers), hexoxy (various isomers), heptoxy (various isomers), octoxy (various isomers), nonoxy (various isomers), decoxy (various isomers), dodecyloxy (various isomers), octadecyloxy (various isomers), etc.

[0326] As R 511 Aryl groups with 6 to 20 carbon atoms, such as phenyl and naphthyl groups, are examples of aryl groups.

[0327] Regarding R 511 The substituents in the aryl group are alkyl groups, such as methylphenyl (various isomers), ethylphenyl (various isomers), propylphenyl (various isomers), butylphenyl (various isomers), pentylphenyl (various isomers), hexylphenyl (various isomers), heptylphenyl (various isomers), octylphenyl (various isomers), nonylphenyl (various isomers), decylphenyl (various isomers), biphenyl (various isomers), dimethylphenyl (various isomers), diethylphenyl (various isomers), dipropylphenyl (various isomers), dibutylphenyl (various isomers), dipentylphenyl (various isomers), dihexylphenyl (various isomers), diheptylphenyl (various isomers), triphenyl (various isomers), trimethylphenyl (various isomers), triethylphenyl (various isomers), tripropylphenyl (various isomers), tributylphenyl (various isomers), etc.

[0328] As R 511Aromatic oxy groups containing 6 to 20 carbon atoms include, for example, phenoxy, methylphenoxy (various isomers), ethylphenoxy (various isomers), propylphenoxy (various isomers), butylphenoxy (various isomers), pentylphenoxy (various isomers), hexylphenoxy (various isomers), heptylphenoxy (various isomers), octylphenoxy (various isomers), nonylphenoxy (various isomers), decylphenoxy (various isomers), and phenylphenoxy (various isomers). Dimethylphenoxy (various isomers), diethylphenoxy (various isomers), dipropylphenoxy (various isomers), dibutylphenoxy (various isomers), dipentylphenoxy (various isomers), dihexylphenoxy (various isomers), diheptylphenoxy (various isomers), diphenylphenoxy (various isomers), trimethylphenoxy (various isomers), triethylphenoxy (various isomers), tripropylphenoxy (various isomers), tributylphenoxy (various isomers), etc.

[0329] As R 511 Aryl groups containing 7 to 20 carbon atoms include, for example, phenylmethyl, phenylethyl (various isomers), phenylpropyl (various isomers), phenylbutyl (various isomers), phenylpentyl (various isomers), phenylhexyl (various isomers), phenylheptyl (various isomers), phenyloctyl (various isomers), phenylnonyl (various isomers), etc.

[0330] As R 511 Arylalkyloxy groups with 7 to 20 carbon atoms include, for example, phenylmethoxy, phenylethoxy (various isomers), phenylpropoxy (various isomers), phenylbutoxy (various isomers), phenylpentoxy (various isomers), phenylhexyloxy (various isomers), phenylheptoxy (various isomers), phenyloctoxy (various isomers), and phenylnonoxy (various isomers).

[0331] [A 511 ]

[0332] Ring A 511 It is an aromatic hydrocarbon ring with 6 to 20 carbon atoms. Ring A 511 It can be a single ring, a multi-ring, or a fused ring.

[0333] As ring A 511 Specifically, examples include benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, tetraphenylene rings, 1,2-benzophenanthrene rings, pyrene rings, triphenylene rings, cyclopentadiene rings, chamomile rings, heptane rings, indole rings, biphenylene rings, acenaphthene rings, acephenanthrene rings, and acephenanthrene rings. Among these, ring A... 511 Preferably, it contains a benzene ring, a naphthalene ring, or an anthracene ring, with a benzene ring being more preferred.

[0334] In addition, these rings can have the aforementioned R. 511 Other substituents. As R 511 Other substituents, such as those with R, can be cited. 511 The same group as the one illustrated in the example. R 511 and R 511 Other substituents are composed of different functional groups.

[0335] [n511]

[0336] n511 indicates the substituent R 511 The number is an integer between 1 and 10.

[0337] In general formula (V-1), ring A 511 Compounds that are benzene rings include, for example, compounds represented by the following general formula (V-1-1) (hereinafter sometimes referred to as "hydroxy compounds (V-1-1)").

[0338] [Chemistry 43]

[0339]

[0340] (In general formula (V-1-1), R) 512 ~R 516 Each independently of the above R 511 same.)

[0341] Among them, R is preferred. 512 ~R 516 At least one of them is a hydrogen atom, and more preferably R 512 ~R 516 It consists entirely of hydrogen atoms.

[0342] Preferred hydroxyl compounds (V-1-1) include, for example, phenol, 2-ethylphenol, 2-propylphenol (various isomers), 2-butylphenol (various isomers), 2-pentylphenol (various isomers), 2-hexylphenol (various isomers), 2-heptylphenol (various isomers), 2-phenylphenol, 2,6-dimethylphenol, 2,4-diethylphenol, 2,6-diethylphenol, 2,4-dipropylphenol (various isomers), 2,6-dipropylphenol (various isomers), 2,4-dibutylphenol (various isomers), 2,4-dipentylphenol (various isomers), 2,4-dihexylphenol (various isomers), 2,4-diheptylphenol (various isomers), 2-methyl-6-ethylphenol, 2-methyl-6-ethylphenol, 2-methyl-6-ethylphenol, 2-ethyl ... -Propylphenol (various isomers), 2-methyl-6-butylphenol (various isomers), 2-methyl-6-pentylphenol (various isomers), 2-ethyl-6-propylphenol (various isomers), 2-ethyl-6-butylphenol (various isomers), 2-ethyl-6-pentylphenol (various isomers), 2-propyl-6-butylphenol (various isomers), 2-ethyl-4-methylphenol (various isomers), 2-ethyl-4-propylphenol (various isomers), 2-ethyl-4-butylphenol (various isomers), 2-ethyl-4-pentylphenol (various isomers), 2-ethyl-4-hexylphenol (various isomers), 2-ethyl-4-heptylphenol (various isomers), 2-ethyl-4-octylphenol (various isomers), 2-ethyl 2-Propyl-4-phenylphenol (various isomers), 2-ethyl-4-cumylphenol (various isomers), 2-propyl-4-methylphenol (various isomers), 2-propyl-4-ethylphenol (various isomers), 2-propyl-4-butylphenol (various isomers), 2-propyl-4-pentylphenol (various isomers), 2-propyl-4-hexylphenol (various isomers), 2-propyl-4-heptylphenol (various isomers), 2-propyl-4-octylphenol (various isomers), 2-propyl-4-phenylphenol (various isomers), 2-propyl-4-cumylphenol (various isomers), 2-butyl-4-methylphenol (various isomers), 2-butyl-4-ethylphenol (various isomers), 2-butyl-4-propylphenol (various isomers), 2- Butyl-4-pentylphenol (various isomers), 2-butyl-4-hexylphenol (various isomers), 2-butyl-4-heptylphenol (various isomers), 2-butyl-4-octylphenol (various isomers), 2-butyl-4-phenylphenol (various isomers), 2-butyl-4-cumylphenol (various isomers), 2-pentyl-4-methylphenol (various isomers), 2-pentyl-4-ethylphenol (various isomers), 2-pentyl-4-propylphenol (various isomers), 2-pentyl-4-butylphenol (various isomers), 2-pentyl-4-hexylphenol (various isomers), 2-pentyl-4-heptylphenol (various isomers), 2-pentyl-4-octylphenol (various isomers), 2-pentyl-4-phenylphenol (various isomers)2-Pentyl-4-cumylphenol (various isomers), 2-Hexyl-4-methylphenol (various isomers), 2-Hexyl-4-ethylphenol (various isomers), 2-Hexyl-4-propylphenol (various isomers), 2-Hexyl-4-butylphenol (various isomers), 2-Hexyl-4-pentylphenol (various isomers), 2-Hexyl-4-heptylphenol (various isomers), 2-Hexyl-4-octylphenol (various isomers), 2-Hexyl-4-phenylphenol (various isomers), 2-Hexyl-4-cumylphenol (various isomers), 2-Heptyl-4-methylphenol (various isomers), 2-Heptyl-4-ethylphenol (various isomers), 2-Heptyl-4-propylphenol (various isomers), 2-Heptyl-4-butylphenol (various isomers) ), 2-heptyl-4-pentylphenol (various isomers), 2-heptyl-4-hexylphenol (various isomers), 2-heptyl-4-octylphenol (various isomers), 2-heptyl-4-phenylphenol (various isomers), 2-heptyl-4-cumylphenol (various isomers), 2,4,6-trimethylphenol, 2,6-dimethyl-4-ethylphenol, 2,6-dimethyl-4-propylphenol (various isomers), 2,6-dimethyl-4-butylphenol (various isomers), 2,6-dimethyl-4-pentylphenol (various isomers), 2,6-dimethyl-4-hexylphenol (various isomers), 2,6-dimethyl-4-phenylphenol, 2,6-dimethyl-4-cumylphenol, 2,4,6-triethylphenol, 2,6- Diethyl-4-methylphenol, 2,6-diethyl-4-propylphenol (various isomers), 2,6-diethyl-4-butylphenol (various isomers), 2,6-diethyl-4-pentylphenol (various isomers), 2,6-diethyl-4-hexylphenol (various isomers), 2,6-diethyl-4-phenylphenol, 2,6-diethyl-4-cumylphenol, 2,4,6-tripropylphenol (various isomers), 2,6-dipropyl-4-ethylphenol (various isomers), 2,6-dipropyl-4-methylphenol (various isomers), 2,6-dipropyl-4-butylphenol (various isomers), 2,6-dipropyl-4-pentylphenol (various isomers), 2,6-dipropyl-4-hexylphenol (various isomers), 2, 6-Dipropyl-4-phenylphenol (various isomers), 2,6-dipropyl-4-cumylphenol (various isomers), 2,4-dimethyl-6-ethylphenol, 2-methyl-4,6-diethylphenol, 2-methyl-4-propyl-6-ethylphenol (various isomers), 2-methyl-4-butyl-6-ethylphenol (various isomers), 2-methyl-4-pentyl-6-ethylphenol (various isomers), 2-methyl-4-hexyl-6-ethylphenol (various isomers), 2-methyl-4-phenyl-6-ethylphenol (various isomers), 2-methyl-4-cumyl-6-ethylphenol (various isomers), 2,4-dimethyl-6-propylphenol (various isomers), 2-methyl-4,6-dipropylphenol (various isomers)2-Methyl-4-ethyl-6-propylphenol (various isomers), 2-methyl-4-butyl-6-propylphenol (various isomers), 2-methyl-4-pentyl-6-propylphenol (various isomers), 2-methyl-4-hexyl-6-propylphenol (various isomers), 2-methyl-4-phenyl-6-propylphenol (various isomers), 2-methyl-4-cumyl-6-propylphenol (various isomers), 2,4-dimethyl-6-butylphenol, 2-methyl-4,6-dibutylphenol, 2-methyl-4-propyl-6-butylphenol (various isomers), 2-methyl-4-ethyl-6-butylphenol (various isomers), 2-methyl-4-pentyl-6-butylphenol (various isomers), 2-methyl-4-hexyl-6-butylphenol (various isomers) 2-Methyl-4-phenyl-6-butylphenol (various isomers), 2-methyl-4-cumyl-6-butylphenol (various isomers), 2,4-dimethyl-6-pentylphenol, 2-methyl-4,6-dipentylphenol, 2-methyl-4-propyl-6-pentylphenol (various isomers), 2-methyl-4-butyl-6-pentylphenol (various isomers), 2-methyl-4-ethyl-6-pentylphenol (various isomers), 2-methyl-4-hexyl-6-pentylphenol (various isomers), 2-methyl-4-phenyl-6-pentylphenol (various isomers), 2-methyl-4-cumyl-6-pentylphenol (various isomers), 2,4-dimethyl-6-hexylphenol, 2-methyl-4,6-dihexylphenol 2-Methyl-4-propyl-6-hexylphenol (various isomers), 2-Methyl-4-butyl-6-hexylphenol (various isomers), 2-Methyl-4-pentyl-6-hexylphenol (various isomers), 2-Methyl-4-ethyl-6-hexylphenol (various isomers), 2-Methyl-4-phenyl-6-hexylphenol (various isomers), 2-Methyl-4-cumyl-6-hexylphenol (various isomers), 2-Ethyl-4-methyl-6-propylphenol (various isomers), 2,4-diethyl-6-propylphenol (various isomers), 2-Ethyl-4,6-propylphenol (various isomers), 2-Ethyl-4-butyl-6-propylphenol (various isomers), 2-Ethyl-4-pentyl-6-propylphenol (various isomers) ), 2-Ethyl-4-hexyl-6-propylphenol (various isomers), 2-Ethyl-4-heptyl-6-propylphenol (various isomers), 2-Ethyl-4-octyl-6-propylphenol (various isomers), 2-Ethyl-4-phenyl-6-propylphenol (various isomers), 2-Ethyl-4-cumyl-6-propylphenol (various isomers), 2-Ethyl-4-methyl-6-butylphenol (various isomers), 2,4-diethyl-6-butylphenol (various isomers), 2-Ethyl-4,6-butylphenol (various isomers), 2-Ethyl-4-propyl-6-butylphenol (various isomers), 2-Ethyl-4-pentyl-6-butylphenol (various isomers), 2-Ethyl-4-hexyl-6-butylphenol (various isomers)2-Ethyl-4-heptyl-6-butylphenol (various isomers), 2-Ethyl-4-octyl-6-butylphenol (various isomers), 2-Ethyl-4-phenyl-6-butylphenol (various isomers), 2-Ethyl-4-cumyl-6-butylphenol (various isomers), 2-Ethyl-4-methyl-6-pentylphenol (various isomers), 2,4-diethyl-6-pentylphenol (various isomers), 2-Ethyl-4,6-pentylphenol (various isomers), 2-Ethyl-4-butyl-6-pentylphenol (various isomers), 2-Ethyl-4-propyl-6-pentylphenol (various isomers), 2 -Ethyl-4-hexyl-6-pentylphenol (various isomers), 2-Ethyl-4-heptyl-6-pentylphenol (various isomers), 2-Ethyl-4-octyl-6-pentylphenol (various isomers), 2-Ethyl-4-phenyl-6-pentylphenol (various isomers), 2-Ethyl-4-cumyl-6-pentylphenol (various isomers), 2-Ethyl-4-methyl-6-hexylphenol (various isomers), 2,4-diethyl-6-hexylphenol (various isomers), 2-Ethyl-4,6-hexylphenol (various isomers), 2-Ethyl-4-propyl-6-hexylphenol (various isomers), 2- Ethyl-4-pentyl-6-hexylphenol (various isomers), 2-ethyl-4-butyl-6-hexylphenol (various isomers), 2-ethyl-4-heptyl-6-hexylphenol (various isomers), 2-ethyl-4-octyl-6-hexylphenol (various isomers), 2-ethyl-4-phenyl-6-hexylphenol (various isomers), 2-ethyl-4-cumyl-6-hexylphenol (various isomers), 2-propyl-4-methyl-6-butylphenol (various isomers), 2,4-dipropyl-6-butylphenol (various isomers), 2-propyl-4,6-butylphenol (various isomers), 2-propyl The following are isomers of 2-propyl-4-ethyl-6-butylphenol: 2-propyl-4-pentyl-6-butylphenol, 2-propyl-4-hexyl-6-butylphenol, 2-propyl-4-heptyl-6-butylphenol, 2-propyl-4-octyl-6-butylphenol, 2-propyl-4-phenyl-6-butylphenol, cumylphenol, 2-propyl-4-cumyl-6-butylphenol, 2,4-dicumylphenol, methoxyphenol, and ethoxyphenol. Among these, phenol, cumylphenol, methoxyphenol, or ethoxyphenol are preferred.

[0343] Methods for the manufacture of isocyanate compounds

[0344] The method for producing the isocyanate compound in this embodiment includes distilling and purifying a reaction solution containing the isocyanate compound (II) in the presence of the carbonyl compound (I) to continuously recover the isocyanate compound (II) as a gaseous component.

[0345] In the method for manufacturing isocyanate compounds according to this embodiment, by using the carbonyl compound (I) described above, the solidification of byproducts on the apparatus during the manufacturing of isocyanate compound (II) can be prevented, thereby increasing the yield of isocyanate compound (II).

[0346] The method for manufacturing the isocyanate compound of this embodiment will be described in detail below.

[0347] The isocyanate compound (II) is obtained by thermally decomposing the above-mentioned carbamate compound (VI) in the presence of the above-mentioned carbonate (IV).

[0348] [Thermal decomposition process]

[0349] In the thermal decomposition process, isocyanate (II) is obtained by thermally decomposing urethane compound (VI) in the presence of carbonate (IV) as a solvent. During the thermal decomposition reaction, side reactions represented by formulas (B) to (E) occur. The generated isocyanurate, carbodiimide, and urea carbamate groups act as crosslinking sites, potentially generating high molecular weight components and causing the formation of solid substances and an increase in liquid viscosity. By having the carbonyl compound (I) present in the thermal decomposition reaction system, carbonyl compound (I) acts as a good solvent for the aforementioned high molecular weight components and as a capping agent, suppressing the high molecular weight formation of byproducts. This effectively inhibits the formation of solid substances and the increase in liquid viscosity during the thermal decomposition reaction.

[0350] Carbonate (IV) can be supplied to the reactor before the reaction begins, during the reaction, or both. Preferably, it is supplied to the reactor before the reaction begins.

[0351] In the thermal decomposition process, from the perspective of suppressing side reactions, it is preferable to use a large amount (molar amount) of carbonate (IV) as a solvent. Considering the size of the reactor, the amount is preferably 0.001 times to 100 times, more preferably 0.01 times to 80 times, and even more preferably 0.1 times to 50 times, in terms of the stoichiometric ratio relative to the carbamate compound.

[0352] When manufacturing a carbamate compound by the method described later, if the carbamate compound contains carbonate (IV), carbonate (IV) can be used directly, or carbonate (IV) can be newly added to the carbamate compound (VI).

[0353] The reaction temperature is typically between 100°C and 400°C. Higher temperatures are preferred to increase the reaction rate. However, at high temperatures, the aforementioned side reactions may occur due to one or more compounds selected from the group consisting of urethane compounds and isocyanate compounds as products. Therefore, the reaction temperature is preferably between 130°C and 300°C, more preferably between 150°C and 280°C. To maintain a constant reaction temperature, known cooling or heating devices can be installed in the reactor.

[0354] Furthermore, the reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or increased pressure, typically above 20 Pa (1×10⁻⁶). 6 The range is below Pa.

[0355] There are no particular restrictions on the reaction time (retention time in the case of continuous methods), which is usually 0.001 hours to 100 hours, preferably 0.01 hours to 50 hours, and more preferably 0.1 hours to 10 hours.

[0356] A catalyst may be used, and the amount of catalyst used relative to the mass of the carbamate compound is preferably 0.01% to 30% by mass, more preferably 0.5% to 20% by mass.

[0357] Examples of organometallic catalysts include dibutyltin dilaurate, lead octanoate, and stannous octanoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine, and triethylamine. Among these, dibutyltin dilaurate, lead octanoate, and stannous octanoate are particularly suitable. These compounds can be used alone or in mixtures of two or more.

[0358] As described above, the thermal decomposition reaction is an equilibrium reaction in which urethane compound (VI) generates the corresponding isocyanate compound (II) and hydroxyl compound. Therefore, in order to efficiently obtain isocyanate compound (II) in the thermal decomposition reaction, it is preferable to remove the hydroxyl compound, which is a product of the thermal decomposition reaction, from the thermal decomposition reaction system as a gaseous component by means such as distillation.

[0359] [Isocyanate composition preparation process]

[0360] Since the reaction solution obtained in the above-described thermal decomposition process contains carbonyl compound (I), this reaction solution can be used in the purification process described later as a reaction solution (isocyanate composition) containing isocyanate compound (II) and carbonyl compound (I). Alternatively, a mixture (isocyanate composition) formed by mixing the carbonyl compound (I) obtained in the "method for manufacturing carbonyl compound" with the reaction solution containing isocyanate compound can be prepared and used in the purification process described later.

[0361] As a component of the isocyanate composition, from the perspective of ensuring good distillation operation in the purification process described later, the value of {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of urea ketimide group)+2×(molar amount of urea formate group)}÷(molar amount of carbonyl compound) is preferably 0.00001 or more and 80.0 or less, more preferably 0.0001 or more and 40.0 or less, and even more preferably 0.001 or more and 8.0 or less.

[0362] [Refining Process]

[0363] In the refining process, isocyanate compounds are refined from the above-mentioned isocyanate composition. Specifically, in the refining process, firstly, components with boiling points lower than those of the isocyanate compounds contained in the isocyanate composition (light boiling components) are removed by distillation (hereinafter referred to as "light boiling separation"). Then, the isocyanate compounds are recovered in the form of gaseous components and separated from components with boiling points higher than those of the isocyanate compounds (high boiling components) (hereinafter referred to as "high boiling separation"). Thus, isocyanate compounds are refined from the isocyanate composition.

[0364] (Light boiling separation process)

[0365] There are no particular limitations on the distillation removal method as long as the light boiling components can be separated in the form of gaseous components. The "light boiling components (light boiling point components)" referred to here are components with boiling points lower than carbonyl compounds. Although they vary depending on the type of compound that becomes the raw material for the manufacture of isocyanate compounds, these light boiling components are mainly one or more compounds selected from the group consisting of carbonates used in the thermal decomposition process and hydroxyl compounds that are by-products in the thermal decomposition reaction.

[0366] The pressure used for distillation to remove light-boiling components varies depending on the type of compound and the reaction temperature. Within the range sufficient to separate the isocyanate compound from the light-boiling components, it can be any of reduced pressure, atmospheric pressure, or pressurized pressure, preferably 20 Pa or higher (1 × 10⁻⁶). 6 Pa or less, more preferably 20 Pa or more, 1×10 4 Pa below, more preferably above 20 Pa, 1×10 3Below 20 Pa, especially preferably above 20 Pa, 1×10 2 Below Pa.

[0367] Regarding the operation time (retention time in the case of continuous methods) for removing light boiling components by distillation, there is no particular limitation within the range that allows for the separation of isocyanate compounds from light boiling components. From the perspective of suppressing side reactions with isocyanate compounds, it is preferably 5 seconds to 100 hours, more preferably 10 seconds to 50 hours, and even more preferably 20 seconds to 10 hours.

[0368] Regarding the temperature for distilling to remove light boiling components, there are no particular limitations within a range that allows the isocyanate compound to be stable and to separate the isocyanate compound from the light boiling components. From the perspective of suppressing the modification of the isocyanate compound, it is preferably 20°C to 300°C, more preferably 30°C to 280°C, and even more preferably 40°C to 250°C.

[0369] (High-boiling-point separation process)

[0370] As long as isocyanates can be separated in the form of gaseous components, there are no particular limitations on the distillation removal method. The "high-boiling component" (high-boiling-point component) referred to here means the component with a boiling point higher than that of isocyanate. Although it varies depending on the type of compound that becomes the raw material for manufacturing isocyanate compounds, this high-boiling component is mainly a carbonyl compound, carbamate compound (III) (isocyanate containing carbamate group) and carbamate compound (VI) (carbamate compound that becomes the raw material for the thermal decomposition process) generated in the thermal decomposition process, and a compound formed by converting a portion of the isocyanate group of the isocyanurate group, carbodiimide group, urea ketimide group and urea carbamate group into at least one functional group selected from the group consisting of isocyanurate group, carbodiimide group, urea ketimide group and urea carbamate group (hereinafter referred to as "isocyanate polymer").

[0371] In the high-boiling separation process, as shown in the following formula (J), the urea-ketone imine group generated by the thermal decomposition process or the light-boiling separation process will be regenerated into isocyanate group and carbodiimide group. Therefore, the recovery rate of isocyanate compound recovered in the gas phase may exceed 100% by mass.

[0372] [Chemistry 44]

[0373]

[0374] (In formula (J), R) m and R n Each of these is an organic group with a valence of two or more.

[0375] On the other hand, in the high-boiling separation process, the high-boiling components are concentrated and solidified by distillation to remove isocyanate compounds, which may make it difficult to operate continuously and recover isocyanate compounds in high yield. This is because the isocyanate (isocyanate polymer) obtained by converting a portion of the isocyanate group into at least one functional group selected from the group consisting of isocyanurate group, carbodiimide group, urea ketimide group, and urea carbamate group has a high molecular weight; during high-boiling separation, the carbodiimide group generated by the above formula (J) bonds with the isocyanate group of the isocyanate polymer to form urea ketimide group (the reverse reaction of the above formula (J)), and the isocyanate polymers bond with each other, thereby having a high molecular weight.

[0376] Carbonyl compounds (I) have higher boiling points and fewer crosslinking points than isocyanate compounds, thus functioning as solvents in high-boiling-point separation processes. Alternatively, they can bond with carbodiimide groups, preventing isocyanate polymers from bonding together and resulting in higher molecular weights. Through these effects, high-boiling-point separation processes can be well-operated, and isocyanate compounds can be recovered in high yields.

[0377] The pressure used to separate high-boiling components varies depending on the type of compound and the reaction temperature. Within the range capable of separating isocyanate compounds from light-boiling components, it can be any of reduced pressure, atmospheric pressure, or pressurized pressure, preferably 0.1 Pa or higher and 1 × 10⁻⁶ Pa. 6 Pa or less, more preferably 1 Pa or more, 1 × 10 Pa 4 Pa or less, more preferably 5 Pa or more, 1×10 3 Below Pa.

[0378] Regarding the operating time (retention time in the case of continuous methods) for separating high-boiling components, there are no particular limitations within the range that allows for the separation of isocyanate compounds and light-boiling components. From the perspective of suppressing side reactions with isocyanate compounds, it is preferably 5 seconds to 100 hours, more preferably 10 seconds to 50 hours, further preferably 15 seconds to 10 hours, particularly preferably 20 seconds to 1 hour, and most preferably 25 seconds to 10 minutes.

[0379] Regarding the temperature for separating high-boiling components, there are no particular limitations within the range where the isocyanate compound is stable and the separation of the isocyanate compound and the light-boiling components can be carried out. From the perspective of suppressing the modification of the isocyanate compound, it is preferably 20°C to 250°C, more preferably 30°C to 230°C, and even more preferably 40°C to 200°C.

[0380] [Settings and Materials]

[0381] Regarding the materials used for reactors and pipelines in the thermal decomposition and refining processes, any known material may be used, as long as it does not adversely affect the urethane compounds, the hydroxyl compounds and isocyanate compounds that are the products, or the carbonates that are the solvents. SUS304, SUS316, SUS316L, etc. are low in cost and can be preferred.

[0382] There are no particular restrictions on the form of the reactor; known tank-shaped or tower-shaped reactors can be used. In the thermal decomposition reaction and the subsequent distillation removal of light-boiling components, a reactor equipped with pipelines for discharging the generated low-boiling-point mixture containing hydroxyl compounds as a gaseous component from the reactor, and for discharging part or all of the mixture containing unreacted carbamate compounds and compounds not discharged as a gaseous component from the reactor as a liquid component. Such reactors can be made by various known methods, including reactors such as stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tube reactors, continuous multi-stage distillation columns, packed columns, thin-film evaporators, reactors with internal supports, forced circulation reactors, falling film evaporators, drip evaporators, trickle bed reactors, bubble columns, and combinations thereof.

[0383] From the perspective of separating the generated hydroxyl compound from the isocyanate compound, it is preferable to use a stirred tank equipped with a distillation column or a multi-stage stirred tank, and it is even more preferable to use a structure with a large gas-liquid contact area that allows the generated low-boiling-point component to move rapidly into the gas phase.

[0384] In the purification process of the isocyanate composition, a reactor equipped with pipelines for discharging the light-boiling component as a gaseous component and discharging part or all of the mixture containing the undischarged compound as a liquid component from the reactor is preferably used in the light-boiling separation process. Such a reactor can be made by various known methods, including reactors such as stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tube reactors, continuous multi-stage distillation columns, packed columns, thin-film evaporators, reactors with internal supports, forced circulation reactors, falling film evaporators, drip evaporators, trickle bed reactors, bubble columns, and combinations thereof.

[0385] Furthermore, in the purification process of the isocyanate composition, a reactor equipped with pipelines for discharging the isocyanate compound as a gaseous component from the reactor and discharging part or all of the mixture containing the discharged compound as a liquid component from the reactor is preferably used in the high-boiling separation process. Such reactors can be made by various known methods, including reactors such as stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tube reactors, continuous multi-stage distillation columns, packed columns, thin-film evaporators, reactors with internal supports, forced circulation reactors, falling film evaporators, drip evaporators, trickle bed reactors, bubble columns, and combinations thereof.

[0386] Next, the various raw materials used in the method for manufacturing the isocyanate compound of this embodiment will be described in detail below.

[0387] <Method for manufacturing carbamate compound (VI)>

[0388] As a carbamate compound (VI), as exemplified in the above-described "Method for Manufacturing Carbonyl Compounds".

[0389] As a method for manufacturing urethane compound (VI), a preferred method is one using a carbonate derivative and an amine compound, or a method using a carbonate derivative, a hydroxyl compound, and an amine compound. It should be noted that, regarding the hydroxyl compound used as a raw material for manufacturing urethane compound (VI), it is preferable to use the same compound as the hydroxyl compound (V) described above.

[0390] [Carbonated derivatives]

[0391] Examples of carbonic acid derivatives include urea and carbonates.

[0392] Regarding the carbonate used as a raw material for manufacturing carbamate compound (VI), it is preferable to use the same substance as the carbonate (IV) described above. Among them, urea, diphenyl carbonate, or dibutyl carbonate are preferred as carbonate derivatives, and urea or diphenyl carbonate are more preferred.

[0393] [Amine compounds]

[0394] As an amine compound, compounds represented by the following general formula (VII) are preferred, for example (hereinafter sometimes referred to as "amine compound (VII)").

[0395] [Chemistry 45]

[0396]

[0397] (In general formula (VII), R) 71 For organic groups with an n71 valence, the following relationship is satisfied: R71 =R 61 (where n71 is an integer greater than 2 and less than 8, satisfying the relation: n71 = n61.)

[0398] (R 71 )

[0399] R 71 For organic groups with an n71 valence, the following relationship is satisfied: R 71 =R 61 That is, R 71 With the above R 61 same.

[0400] Among them, as R 71 Preferably, it can have one or more ester groups or less than four nitrogen atoms, and be aliphatic hydrocarbon groups with a carbon number of 1 or more than 20 and a valence of 2 to 4 or a valence of 6 to 20 or a valence of 2 to 3 or a valence of 3.

[0401] Additionally, as R 71 Specifically, it is preferred to be a group represented by any one of the above formulas (Ia-1) to (Ia-24), and more preferably a group represented by formulas (Ia-1), (Ia-2), (Ia-3), (Ia-14), (Ia-18) or (Ia-19).

[0402] (n71)

[0403] n71 represents the number of amino groups, satisfying the relationship: n71 = n61. n71 is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4.

[0404] Preferred amine compounds (VII) include, for example, 4-aminomethyl-1,8-octanediamine, 4,4'-diaminodiphenylmethane, lysine β-aminoethyl ester, lysine methyl ester, 4,4'-methylenebis(cyclohexylamine), and 1,3-di(aminomethyl)cyclohexane.

[0405] Isocyanate Compositions

[0406] The isocyanate composition of this embodiment contains, relative to the total mass of the isocyanate composition:

[0407] Isocyanate compounds of 97% or more by mass; and

[0408] 2.0 ppm or more, 1.0 × 10 4 Carbonyl compounds represented by the following general formula (I) in the mass of less than ppm (hereinafter sometimes referred to as "carbonyl compound (I)").

[0409] The isocyanate compound mentioned above is a different compound from the carbonyl compound mentioned above.

[0410] [Chemistry 46]

[0411]

[0412] (In general formula (I), R) 11 For organic groups with a valence of (n11+n12), R 12 An organic group with a monovalent oxidation state. n11 is an integer between 1 and 8, n12 is an integer between 0 and 7, and the sum of n11 and n12 is an integer between 2 and 8.

[0413] Generally, in compounds containing unsaturated bonds, these bonds tend to be easily oxidized, and unsaturated compounds, as impurities, can easily cause discoloration. However, carbonyl compounds (I) function effectively during the storage of isocyanate compositions, enhancing their stability without causing discoloration. This effect is presumably due to the reactivity of the carbonyl group in carbonyl compound (I) with water and oxygen, inhibiting the modification reactions of the isocyanate composition caused by water and oxygen. Furthermore, since carbonyl compound (I) possesses a large number of carbon-oxygen unsaturated bonds, it tends to further enhance the aforementioned effect.

[0414] To suppress the modification reaction of the isocyanate compound, it is preferable to increase the content of carbonyl compound (I). However, if the content is too high, discoloration caused by unsaturated bonds, as described above, may occur, potentially impairing the appearance during use. Therefore, the lower limit of the carbonyl compound (I) content relative to the total mass of the isocyanate composition is 2.0 ppm by mass, preferably 3.0 ppm by mass, more preferably 5.0 ppm by mass, and even more preferably 10 ppm by mass. On the other hand, the upper limit of the carbonyl compound (I) content relative to the total mass of the isocyanate composition is 1.0 × 10⁻⁶. 4 Mass ppm, preferably 3.0 × 10 3 Mass ppm, more preferably 1.0 × 10 3 Mass (ppm)

[0415] That is, the content of carbonyl compound (I) relative to the total mass of the isocyanate composition is 2.0 ppm or more (1.0 × 10⁻¹⁰). 4 Below ppm by mass, preferably above 3.0 ppm by mass (3.0 × 10⁻¹⁰) 3 Below 1.0 ppm by mass, more preferably 5.0 ppm or above, 1.0 × 10⁻⁶ 3 Below 10 ppm by mass, more preferably above 10 ppm by mass, 1.0 × 10 3 Mass below ppm.

[0416] By setting the content of carbonyl compound (I) to the lower limit or above mentioned above, the modification reaction of isocyanate compound can be suppressed. On the other hand, by setting it to the upper limit or below mentioned above, the coloring caused by unsaturated bonds can be suppressed and the appearance can be well maintained.

[0417] The content of the isocyanate compound is 97% by mass or more, preferably 98% by mass or more, and more preferably 99% by mass or more relative to the total mass of the isocyanate composition. By setting the content of the isocyanate compound to the lower limit value mentioned above, a composition that sufficiently contains the isocyanate compound as the target substance can be obtained. On the other hand, the upper limit is not particularly limited and can be less than 100% by mass.

[0418] The components of the isocyanate composition of this embodiment will be described in detail below.

[0419] <Carbonyl Compounds (I)>

[0420] Carbonyl compound (I) is a compound represented by the following general formula (I).

[0421] [Chemistry 47]

[0422]

[0423] (In general formula (I), R) 11 For organic groups with a valence of (n11+n12), R 12 An organic group with a monovalent oxidation state. n11 is an integer between 1 and 8, n12 is an integer between 0 and 7, and the sum of n11 and n12 is an integer between 2 and 8.

[0424] [R 11 R 12 ]

[0425] R 11 and R 12 As described in the aforementioned "Carbonyl Compounds".

[0426] [n11 and n12]

[0427] n11 is an integer greater than 1 and less than 8.

[0428] n12 represents the number of isocyanate groups, which is an integer between 0 and 7.

[0429] The sum of n11 and n12 (n11+n12) is an integer of 2 to 8, preferably an integer of 2 to 6, more preferably an integer of 2 to 5, and even more preferably an integer of 3 to 4. Generally, the larger the value of (n11+n12), the more crosslinking points (isocyanate groups) there are per carbonyl compound molecule, and the more structures that help prevent coloring and isocyanate modification. Therefore, the crosslinking density increases when the polymer is produced, which can shorten the curing time, increase the hardness of the polymer, and suppress coloring and isocyanate modification. It should be noted that "increased crosslinking density" here refers to a decrease in the average molecular chain length between crosslinking points. On the other hand, in the manufacture of carbonyl compounds, heating the highly reactive isocyanate group will cause a modification reaction, which will become the cause of solidification and blockage in the device. Therefore, from the perspective of carbonyl compound synthesis, it is preferable that (n11+n12) is 6 or less, more preferably (n11+n12) is 5 or less, and even more preferably (n11+n12) is 4 or less.

[0430] Preferred carbonyl compounds (I) include, for example, compounds represented by formulas (I-1a) to (I-24b) (hereinafter sometimes referred to as "carbonyl compound (I-1a)" etc.). It should be noted that carbonyl compounds (I-1a) to (I-1c), carbonyl compounds (I-2a) to (I-2c), carbonyl compounds (I-3a) to (I-3c), carbonyl compounds (I-4a) to (I-4c), carbonyl compounds (I-5a) to (I-5c), carbonyl compounds (I-6a) to (I-6c), carbonyl compounds (I-7a) to (I-7b), and carbonyl compounds (I-8a) to (I-1c) are also preferred. -8b), carbonyl compounds (I-9a) to (I-9b), carbonyl compounds (I-10a) to (I-10b), carbonyl compounds (I-11a) to (I-11b), carbonyl compounds (I-12a) to (I-12b), carbonyl compounds (I-22a) to (I-22b), or carbonyl compounds (I-24a) to (I-24b) can be prepared as mixtures or as individual compounds.

[0431] Furthermore, carbonyl compounds (I) can be used alone or in combination of two or more. When two or more carbonyl compounds (I) are used in combination, since each carbonyl compound (I) has an equal effect on improving the stability of the isocyanate compound, they can be mixed in any proportion.

[0432] [Chemistry 48]

[0433]

[0434] [Chemistry 49]

[0435]

[0436] [Transformation 50]

[0437]

[0438] [Chemistry 51]

[0439]

[0440] [Chemistry 52]

[0441]

[0442] [Chemistry 53]

[0443]

[0444] [Chemistry 54]

[0445]

[0446] [Chemistry 55]

[0447]

[0448] <Isocyanate compounds>

[0449] As isocyanate compounds, compounds represented by the following general formula (II) are preferred (hereafter referred to as "isocyanate compound (II)").

[0450] [Chemistry 56]

[0451]

[0452] (In general formula (II), R) 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 (where n21 is an integer greater than 2 and less than 8, satisfying the relation: n21 = n11 + n12.)

[0453] [R 21 [n21]

[0454] R 21 n21 is as described in the section on isocyanate compounds in the aforementioned "Methods for Manufacturing Carbonyl Compounds".

[0455] Preferred isocyanate compounds (II) include, for example, 4-isocyanate methyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanate ethyl-2,6-diisocyanate hexanoate (LTI), lysine methyl ester diisocyanate (LDI), diisocyanate pentane (PDI), diisocyanate hexane (HDI), methylene bis(cyclohexyl isocyanate) (HMDI), 1,3-bis(isocyanate methyl)cyclohexane (HXDI), 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), diisocyanate xylene (XDI), diisocyanate diphenylmethane (MDI), and diisocyanate toluene (TDI).

[0456] The isocyanate composition of this embodiment preferably further contains 2.0 ppm or more of 1.0 × 10⁻⁶ ppm by weight. 4 The compounds selected from the group consisting of carbamate compounds and carbonates with a mass of less than ppm are one or more compounds.

[0457] The urethane and carbonate compounds also exhibit the same effects as the carbonyl compound (I) described above. To suppress the modification reaction of the isocyanate compounds, it is preferable to increase their content in the isocyanate composition; however, considering color suppression and appearance during use, it is preferable that the content is not excessive. Therefore, the lower limit of the content of each urethane compound and carbonate relative to the total mass of the isocyanate composition is preferably 2.0 ppm by mass, more preferably 3.0 ppm by mass, further preferably 5.0 ppm by mass, and particularly preferably 10 ppm by mass. On the other hand, the upper limit of the content of each urethane compound and carbonate relative to the total mass of the isocyanate composition is preferably 1.0 × 10⁻⁶. 4 Mass ppm, more preferably 3.0 × 10 3 Mass ppm, more preferably 1.0 × 10⁻⁶ 3 Mass (ppm)

[0458] That is, the content of each carbamate compound and carbonate relative to the total mass of the isocyanate composition is preferably 2.0 ppm or more (1.0 × 10⁻¹⁰ ppm). 4 Below ppm by mass, more preferably 3.0 ppm or above, 3.0 × 10⁻⁶ 3 Below ppm by mass, more preferably above 5.0 ppm by mass, 1.0 × 10⁻⁶ 3 Below ppm by mass, preferably above 10 ppm by mass, 1.0 × 10 3 Mass below ppm.

[0459] By setting the contents of the urethane compound and the carbonate to the lower limit or above, the modification reaction of the isocyanate compound can be suppressed. On the other hand, by setting them to the upper limit or below, the coloring caused by unsaturated bonds can be suppressed, and the appearance can be well maintained.

[0460] When the isocyanate composition of this embodiment contains all three compounds—carbonyl compound (I), carbamate compound, and carbonate—the lower limit of the total content of these compounds relative to the total mass of the isocyanate composition is preferably 2.0 ppm by mass, more preferably 3.0 ppm by mass, further preferably 5.0 ppm by mass, and particularly preferably 10 ppm by mass. On the other hand, the upper limit of the total content of these compounds relative to the total mass of the isocyanate composition is preferably 1.0 × 10⁻⁶. 5 Mass ppm, more preferably 1.0 × 10 4 Mass ppm, more preferably 3.0 × 10⁻⁶ 3 Mass ppm, preferably 1.0 × 10⁻⁶ 3 Mass (ppm)

[0461] That is, the total content of carbonyl compound (I), carbamate compound and carbonate is preferably 2.0 ppm or more (1.0 × 10⁻¹) relative to the total mass of the isocyanate composition. 5 Below ppm by mass, more preferably above 3.0 ppm by mass, 1.0 × 10⁻⁶ 4 Below ppm by mass, more preferably above 5.0 ppm by mass, 3.0 × 10⁻⁶ 3 Below ppm by mass, preferably above 10 ppm by mass, 1.0 × 10 3 Mass below ppm.

[0462] By setting the total content of these compounds above the aforementioned lower limit, the modification reaction of isocyanate compounds can be further suppressed. On the other hand, by setting it below the aforementioned upper limit, the coloring caused by unsaturated bonds can be further suppressed, and the appearance can be maintained better.

[0463] <Carbamate Compounds>

[0464] As a carbamate compound, the compound represented by the following general formula (III) is preferred (hereafter referred to as "carbamate compound (III)").

[0465] [Chemistry 57]

[0466]

[0467] (In general formula (III), R) 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R31 =R 11 R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 Let n31 be an integer greater than or equal to 1 and less than or equal to 8, and n32 be an integer greater than or equal to 0 and less than or equal to 7. The sum of n31 and n32 is an integer greater than or equal to 2 and less than or equal to 8, satisfying the relation: n31 + n32 = n11 + n12.

[0468] [R 31 R 31 [n31, n32]

[0469] R 31 R 31 n31 and n32 are as described in the [Carbamate Compounds (III)] section of the above-mentioned "Methods for Manufacturing Carbonyl Compounds".

[0470] Preferred carbamate compounds (III) include, for example, compounds represented by the formulas (III-1a) to (III-24b). It should be noted that carbamate compounds (III-1a) to (III-1c), carbamate compounds (III-2a) to (III-2c), carbamate compounds (III-3a) to (III-3c), carbamate compounds (III-4a) to (III-4c), carbamate compounds (III-5a) to (III-5c), carbamate compounds (III-6a) to (III-6c), carbamate compounds (III-7a) to (III-7b), and carbamate compounds (III- 8a)~(III-8b), carbamate compounds (III-9a)~(III-9b), carbamate compounds (III-10a)~(III-10b), carbamate compounds (III-11a)~(III-11b), carbamate compounds (III-12a)~(III-12b), carbamate compounds (III-22a)~(III-22b), or carbamate compounds (III-24a)~(III-24b) can be prepared as mixtures or as individual compounds.

[0471] [Chem.58]

[0472]

[0473] [Chemistry 59]

[0474]

[0475] [Transformation 60]

[0476]

[0477] [Chemistry 61]

[0478]

[0479] [Chemistry 62]

[0480]

[0481] [Chemistry 63]

[0482]

[0483] [Chemistry 64]

[0484]

[0485] [Chemistry 65]

[0486]

[0487] Furthermore, carbamate compounds (III) can be used alone or in combination of two or more. When two or more carbamate compounds (III) are used in combination, since each carbamate compound (III) has an equivalent effect on improving the stability of the isocyanate compound, they can be mixed in any proportion.

[0488] <carbonate>

[0489] As a carbonate, compounds represented by the following general formula (IV) are preferred (hereafter referred to as "carbonate (IV)").

[0490] [Chemistry 66]

[0491]

[0492] (In general formula (IV), R) 41 and R 42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 。 )

[0493] (R 41 and R 42 )

[0494] R 41 and R 42 As described in the section on <Carbonates> in the aforementioned "Methods for Manufacturing Carbonyl Compounds".

[0495] Preferred carbonates (IV) include, for example, diphenyl carbonate, bis(2-methoxyphenyl) carbonate, bis(2-ethoxyphenyl) carbonate, etc.

[0496] <Method for manufacturing isocyanate compositions>

[0497] The isocyanate composition of this embodiment can be manufactured by mixing an isocyanate compound, a carbonyl compound (I), and, if necessary, one or more compounds selected from the group consisting of a carbamate compound and a carbonate compound, in such a manner as to achieve the above-mentioned amounts.

[0498] Alternatively, the urethane compound represented by the following general formula (VI) (hereinafter sometimes referred to as "urethane compound (VI)") may be thermally decomposed, and the resulting composition containing isocyanate compound (II) may be used as the isocyanate composition of this embodiment.

[0499] [Chemistry 67]

[0500]

[0501] In general formula (VI), R 61 For organic groups with an n61 valence (more than 2 valence but less than 8 valence), satisfying the relationship: R 61 =R 21 That is, R 61 With the above R 21 same.

[0502] In general formula (VI), R 62 For a monovalent organic group, the following relationship is satisfied: R 62 =R 12 That is, R 62 With the above R 12 same.

[0503] n61 represents the number of urethane groups, which is an integer between 2 and 8, satisfying the relationship: n61 = n21. That is, n61 is the same as n21 mentioned above.

[0504] Specifically, the urethane compound (VI) is thermally decomposed in the presence of the aforementioned carbonate (IV) as a solvent, thereby obtaining a composition containing the aforementioned isocyanate compound (II).

[0505] At this point, since hydroxyl compounds are generated as byproducts, it is preferable to carry out thermal decomposition reactions while simultaneously removing and separating these hydroxyl compounds.

[0506] Furthermore, the thermal decomposition reaction is preferably carried out by a continuous method. The continuous method is as follows: a reaction solution containing urethane compound (VI) is continuously fed into a reactor to carry out the thermal decomposition reaction of urethane compound (VI), and the by-product hydroxyl compounds are continuously discharged from the reactor.

[0507] The thermal decomposition temperature varies depending on the type of urethane compound (VI) used, and can be, for example, above 140°C and below 380°C.

[0508] Furthermore, the reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or pressurized pressure. The pressure can be the saturated vapor pressure of the aprotic solvent used, preferably above 20 Pa and 10 × 10⁻⁶ Pa. 6 The range is below Pa.

[0509] There are no particular restrictions on the reaction time (or residence time in the case of a continuous process), which can be between 0.001 hours and 100 hours.

[0510] The aforementioned carbonyl compound (I) is presumed to be a reaction product of isocyanate compound (II) and carbonate (IV), and is believed to be generated under thermal decomposition reaction conditions. Therefore, the isocyanate composition obtained from the thermal decomposition reaction of urethane compound (VI) contains a specific amount of the aforementioned carbonyl compound (I).

[0511] In the thermal decomposition reaction, the above-mentioned carbamate compound (III) can also be considered a reaction intermediate generated from carbamate compound (VI) before becoming the final product, isocyanate compound (II). By stopping the reaction when the content of isocyanate compound (II) reaches a certain amount or more, an isocyanate composition containing carbamate compound (III) as the above-mentioned reaction intermediate can be obtained.

[0512] The isocyanate composition obtained in the thermal decomposition reaction of urethane compound (VI) contains carbonate (IV) as a solvent. When the amount of carbonate (IV) is large, it can be separated from the isocyanate composition by known separation methods such as distillation, so that the content of carbonate (IV) in the isocyanate composition is within a specific range.

[0513] Furthermore, when the isocyanate composition of this embodiment is prepared by mixing an isocyanate compound, a carbonyl compound (I), and, if necessary, one or more compounds selected from the group consisting of carbamate compounds and carbonates in the above-described amounts, the carbonyl compound, carbamate compound, and carbonate can be prepared using the methods described below. Additionally, regarding the isocyanate compound, the substance obtained by thermally decomposing the carbamate compound (VI) can be purified as needed for use.

[0514] [Method for manufacturing carbonyl compound (I)]

[0515] Carbonyl compound (I) is obtained by heating a mixture of isocyanate compound (II) and carbonate (IV), or a mixture of urethane compound (III) or urethane compound (VI) and carbonate (IV), or a mixture of isocyanate compound (II), urethane compound (III) or urethane compound (VI), carbonate (IV) and a hydroxyl compound (hereinafter sometimes referred to as "a mixture of raw materials for carbonyl compound (I)"). The hydroxyl compound referred to herein can be the same substance as the hydroxyl compound that is byproduct of the thermal decomposition reaction of the urethane compound (VI) described above, as detailed below.

[0516] Regarding the amount (molar amount) of carbonate (IV), from the perspective of suppressing side reactions, it is preferable to use a large amount of carbonate solvent. Considering the size of the reactor, the total molar amount of urethane compound (III), urethane compound (VI), and isocyanate compound (II) is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times, in stoichiometric proportions.

[0517] The reaction temperature is typically between 100°C and 400°C. Higher temperatures are preferred to increase the reaction rate. However, at high temperatures, side reactions may occur due to at least one of the carbamate and isocyanate compounds. Therefore, the reaction temperature is preferably between 130°C and 300°C, more preferably between 150°C and 280°C. To maintain a constant reaction temperature, known cooling or heating devices can be installed in the reactor.

[0518] Furthermore, the reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or increased pressure, typically above 20 Pa (1×10⁻⁶). 6 The range is below Pa.

[0519] There are no particular restrictions on the reaction time (retention time in the case of continuous methods), which is usually 0.001 hours to 100 hours, preferably 0.01 hours to 50 hours, and more preferably 0.1 hours to 10 hours.

[0520] In the production of carbonyl compounds based on mixed heating, the formation rate and quantity of carbonyl compounds can be increased by contacting the raw material liquid with stainless steel and then heating it. As for the stainless steel, any material made of SUS316 or SUS304, regardless of its shape, can be used; for example, fillers or metal sheets are preferred. There are no particular limitations on the filler material; DIXON packing, McMAHON packing, Coil pack, MESH RING, CANNON packing, HELIPACK, RASCHIG RING, PRICKLE RING, etc., can be used.

[0521] When setting the volume V of the carbonyl compound feed solution and the surface area A of the stainless steel, the larger the contact area between the feed solution per unit volume and the stainless steel, the faster the carbonyl compound is formed. The preferred value for A / V is 0.001 m. 2 / m 3 The above 100,000m 2 / m 3 The following, or more preferably, is 0.01m 2 / m 3 Above 50,000m 2 / m 3 The following, and more preferably, is 0.1m 2 / m 3 Above 10000m 2 / m 3 the following.

[0522] The reaction method is not particularly limited, but a reactor that can effectively mix the carbonyl compound (I) raw material mixture or the carbonyl compound (I) raw material mixture with stainless steel and can be heated is preferred. For example, a stirring tank or distillation column made of stainless steel is preferred for heating the raw material liquid.

[0523] The light-boiling components of the liquid obtained after heating the carbonyl compound (I) raw material mixture can be removed by distillation. There are no particular limitations on the distillation method as long as the light-boiling components can be separated in the form of gaseous components. Light-boiling components (light-boiling parts) refer to components with boiling points lower than those of the carbonyl compound (I). Although this varies depending on the substance used, these light-boiling components are primarily one or more compounds selected from the group consisting of carbonates (IV), isocyanates (II), and hydroxyl compounds.

[0524] [Method for manufacturing carbamate compound (III)]

[0525] Regarding the carbamate compound (III), there are methods for obtaining it by mixing an isocyanate compound (II) and a hydroxyl compound represented by the above formula (V) (hereinafter sometimes referred to as "hydroxyl compound (V)") and heating it, and methods for obtaining it by thermally decomposing the carbamate compound represented by the above formula (VI).

[0526] [Chemistry 68]

[0527] R 51 -OH (V)

[0528] In general formula (V), R 51 For a monovalent organic group, the following relationship is satisfied: R 51 =R 12 That is, R 51 With the above R 12 same.

[0529] Regarding the mixing ratio when manufacturing by mixing isocyanate compound (II) and hydroxy compound (V) and heating, it is preferable to mix and heat in such a way that the ratio of isocyanate group of isocyanate compound (II) to hydroxyl group of hydroxy compound (V) is (n31+n32):n31.

[0530] The reaction temperature is typically between 40°C and 400°C. Higher temperatures are preferred to increase the reaction rate. However, at high temperatures, side reactions may occur due to at least one of the carbamate and isocyanate compounds. Therefore, the reaction temperature is preferably between 80°C and 300°C, more preferably between 100°C and 250°C. To maintain a constant reaction temperature, known cooling or heating devices can be installed in the reactor.

[0531] Furthermore, the reaction pressure varies depending on the type of compound used and the reaction temperature, and can be any of reduced pressure, atmospheric pressure, or increased pressure, typically above 20 Pa (1×10⁻⁶). 6 The range is below Pa.

[0532] There are no particular restrictions on the reaction time (retention time in the case of continuous methods), which is usually 0.001 hours to 100 hours, preferably 0.01 hours to 50 hours, and more preferably 0.1 hours to 10 hours.

[0533] In the case of manufacturing via thermal decomposition reaction, as described in the method for manufacturing the isocyanate compound (II) above.

[0534] [Method for manufacturing carbonate (IV)]

[0535] Carbonate (IV) can be synthesized using methods described, for example, in Japanese Patent No. 3071008 (Reference 1) and Japanese Patent No. 4137941 (Reference 2). Specifically, carbonate (IV) can be manufactured by a method in which an aromatic monohydroxy compound is reacted with phosgene or a chlorocarbonate of an aromatic monohydroxy compound in the presence of activated carbon while eliminating hydrogen chloride, or by a method comprising the following steps: step (1), reacting an organometallic compound with carbon dioxide to obtain a reaction mixture containing a dialkyl carbonate formed by the reaction; step (2), separating the dialkyl carbonate from the reaction mixture to obtain a residue; step (3), reacting the residue with an alcohol to form at least one organometallic compound and water, and removing the water from the organometallic compound; and step (4), reacting the dialkyl carbonate separated in step (2) with an aromatic hydroxy compound to obtain an aromatic carbonate. It should be noted that the above-mentioned processes (3) and (4) can be performed in the above order or in the opposite order, or in part or in whole at the same time.

[0536] <Applications>

[0537] The isocyanate composition of this embodiment is suitable as a curing agent raw material in fields requiring appearance quality, such as paints for baking, automotive clear coatings, and coil coatings, because it has sufficient suppression of coloring and excellent storage stability.

[0538] Example

[0539] The present invention will be specifically described below based on embodiments, but the scope of the present invention is not limited to these embodiments. In the following text, "%" means "mass %" and "ppm" means "mass ppm".

[0540] <Analytical Methods>

[0541] (1) 1 H-NMR analysis method

[0542] The device used was a JNM-A400FT-NMR system manufactured by Nippon Electronics Co., Ltd., for implementation. 1 H-NMR analysis.

[0543] (1-1) 1 Preparation of samples for H-NMR analysis

[0544] Weigh 0.3g of the sample solution, add 0.7g of deuterated chloroform and 0.05g of dimethyldiphenylsilane as an internal standard, mix thoroughly, and use the resulting solution as the NMR analysis sample.

[0545] (1-2) Quantitative analysis method

[0546] For each standard substance, an analysis was performed, and quantitative analysis of the sample solution was carried out based on the established calibration curve.

[0547] (2) Gas chromatography analysis method

[0548] The analysis was conducted under the following conditions.

[0549] (Measurement conditions)

[0550] Device: GC-2010 manufactured by Shimadzu Corporation

[0551] Column: DB-1

[0552] Diameter 0.25 mm, length 30 m, film thickness 1.0 μm

[0553] Column temperature: 60℃~300℃

[0554] Inlet temperature: 300℃

[0555] Carrier gas: Helium

[0556] Carrier gas flow rate: 40 mL / min

[0557] Detector: FID (Flame Ionization Detector)

[0558] (2-1) Preparation of samples for gas chromatography analysis

[0559] Weigh 1.0 g of the sample solution, add 10 g of acetonitrile and 0.1 g of anisole as an internal standard, mix thoroughly, and use the resulting solution as the sample for gas chromatography analysis.

[0560] (3) Liquid chromatography analysis method

[0561] The analysis was conducted under the following conditions.

[0562] (Measurement conditions)

[0563] Device: Shimadzu Corporation, LC-10AT

[0564] Column: Inertsil ODS

[0565] Particle size 5μm, inner diameter 2.1mm, length 250mm

[0566] Column temperature: 40℃

[0567] Developing solvent: Water / acetonitrile = 90 / 10

[0568] Developing solvent flow rate: 1 mL / min

[0569] Detector: Photodiode array detector

[0570] (3-1) Preparation of samples for liquid chromatography analysis

[0571] Weigh 1.0 g of the sample solution, add 10 g of acetic acid, mix thoroughly, and use the resulting solution as the sample for liquid chromatography analysis.

[0572] (3-2) Quantitative analysis method

[0573] For each standard substance, an analysis was performed, and quantitative analysis of the sample solution was carried out based on the established calibration curve.

[0574] (4) Refining method based on column grading device

[0575] The carbonyl compounds generated were separated under the following conditions.

[0576] (condition)

[0577] Equipment: Yamazen Corporation, EPCLC-AI-580S

[0578] Dissolution position control purification chromatography

[0579] Injection column: M or L

[0580] Main pillar: High-Flash S, M, or L

[0581] Developing solvent: ethyl acetate / hexane

[0582] Developing solvent flow rate: 0 mL / min~80 mL / min

[0583] Detector: UV detector

[0584] It should be noted that, according to 1 The yield of the generated isocyanate compound was calculated from the values ​​determined by H-NMR, GC, and LC, and the value of {3 × (molar amount of isocyanurate group) + 2 × (molar amount of carbodiimide group) + 3 × (molar amount of urea-ketimide group) + 2 × (molar amount of urea-formate group)} ÷ (molar amount of carbonyl compound). Furthermore, the carbonyl compound was quantified based on the LC values.

[0585] <Evaluation Methods>

[0586] [Preservation Test]

[0587] Add 100g of each isocyanate composition to a 200mL screw-top bottle and store at 25°C under a nitrogen atmosphere for 300 days.

[0588] [Rating 1]

[0589] (Black color value)

[0590] The black and gray values ​​before and after storage were measured using a black and gray color measuring instrument.

[0591] [Rating 2]

[0592] 100g of each isocyanate composition after preservation was pressure filtered using a membrane filter with a pore size of 1μm. The residual mass of the filter was determined based on the mass of the filter before and after filtration, and the amount of modification was calculated using the formula shown below.

[0593] (Modified amount (mass%)) = {(Mass of the filtered filter after filtration) - (Mass of the filtered filter before filtration)} × 100 / 100g

[0594] [Example 1-1]

[0595] Process (1-1): Manufacturing process of carbamate compounds

[0596] use Figure 1 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the preparation of the carbamate compounds following Examples 1-1. Figure 1 The apparatus shown.

[0597] With pipeline 14 closed, 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 5.50 kg (58.5 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 5.50 kg (58.5 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reactor 105 equipped with a flow guide plate, and 20.52 kg (95.9 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the solution, a mixture of 4-aminomethyl-1,8-octanediamine and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction solution is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 15.53 kg of phenol is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0598] The resulting solution (hereinafter referred to as "reaction solution (1-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was produced in 99% by mass. The reaction solution (1-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (1-1) was 19.40 kg.

[0599] Process (1-2): Thermal decomposition process of carbamate compounds

[0600] use Figure 2 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the thermal decomposition of the carbamate compounds following Examples 1-1. Figure 2 The apparatus shown.

[0601] With pipeline 24 closed, 19.40 kg of diphenyl carbonate is supplied from storage tank 202 to SUS reaction vessel 201 with baffles via pipeline 22. The temperature of multistage distillation column 203 is raised to 170°C, the jacket temperature of reaction vessel 201 is heated to 228°C, and the pressure is reduced to 14 kPa. 19.40 kg of reaction liquid (1-1) recovered from storage tank 106 in step (1-1) is heated to 120°C and supplied to reaction vessel 201 via pipeline 21 over approximately 15 minutes for thermal decomposition of the carbamate compound. The pressure is adjusted to a range of 8 to 14 kPa, and the phenol generated by thermal decomposition is separated from diphenyl carbonate and the product 1,8-diisocyanate-4-isocyanate-methyloctane (TTI) via distillation column 203, and recovered to storage tank 204 via pipeline 25, condenser A21, and pipeline 27. The reflux ratio at this point is 1.2. After all of the reaction solution (1-1) has been transferred, the phenol discharge is further carried out at an internal temperature of 220°C. Four hours after all of the reaction solution (1-1) has been transferred, the reaction is terminated, and the reaction solution is discharged from pipeline 28 and transferred to storage tank 205. The mass of the reaction solution transferred to storage tank 205 is 18.63 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (1-2)") is purified using a column fractionation device to separate the carbonyl compound. The separated carbonyl compound is a mixture of compounds represented by the following formulas (I-1a) to (I-1c). In addition, the carbonyl compound is... 1 The H-NMR spectrum is shown in Figure 5 .

[0602] [Chemistry 69]

[0603]

[0604] An LC calibration curve was prepared from the obtained carbonyl compound, and the carbonyl compound was quantified using the absolute calibration curve method. In subsequent examples, the separation operation of the carbonyl compound was not performed, and the carbonyl compound was quantified based on the calibration curve.

[0605] In addition, 1 H-NMR and gas chromatography analysis showed that TTI was produced in a yield of 70% by mass, at which point the value of the reaction solution {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of urea-ketimide group)+2×(molar amount of urea-formate group)}÷(molar amount of carbonyl compound) was 3.7.

[0606] Process (1-3): Light-boil separation process

[0607] use Figure 3 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the light-boiling separation following Example 1-1. Figure 3 The apparatus shown.

[0608] The reaction solution (1-2) is continuously fed from storage tank 205 through pipeline 31 at a rate of 3.73 kg / h to the middle section of continuous multistage distillation column 301 for distillation separation of the liquid phase components. The liquid at the bottom of the column is circulated through reboiler A32 and pipeline 33, thereby supplying the heat required for distillation separation. The liquid temperature at the bottom of the continuous multistage distillation column is 220°C, and the pressure at the top of the column is 1.5 kPa. The gas distilled from the top of the continuous multistage distillation column 301 is condensed by condenser A31 through pipeline 32 and continuously discharged into storage tank 302 through pipeline 36. In addition, the gas is continuously discharged into storage tank 303 at a steady-state discharge rate of 1.49 kg / h through pipeline 34. The liquid recovered in storage tank 303 (hereinafter referred to as "reaction solution (1-3)") was 7.45 kg. It was analyzed by NMR, LC and gas chromatography. The results showed that TTI was recovered in a yield of 82% by mass relative to the supplied reaction solution (1-2). The value of the reaction solution at this time was 4.6: {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of urea ketimide group)+2×(molar amount of urea carbamate group)}÷(molar amount of carbonyl compound).

[0609] Process (1-4): High-boiling point separation process

[0610] use Figure 4 The apparatus shown is used for the reaction. It should be noted that the high-boiling separation process following Example 1-1 also uses this apparatus. Figure 4 The apparatus shown.

[0611] The thin-film distillation apparatus 401 (manufactured by KOBELCO ECO-SOLUTIONS, Japan) is heated to 190°C, and the internal pressure is set to 0.3 kPa. The reaction liquid (1-3) recovered from the storage tank 303 in steps (1-3) is supplied to the upper part of the thin-film distillation apparatus 401 via pipeline 41 at approximately 1.0 kg / hour for separation of isocyanate and high-boiling components. The generated gaseous components are transported to the storage tank 402 via pipeline 42 and condenser A41. The liquid recovered from the storage tank 402 is 3.35 kg, and the TTI recovery rate is 121% by mass. It should be noted that the reason why the TTI recovery rate exceeds 100% by mass is that a portion of the isocyanate modified product generated in the thermal decomposition step or the light-boiling separation step is regenerated as TTI.

[0612] [Examples 1-2]

[0613] Process (2-2): Thermal decomposition process of carbamate compounds

[0614] Using 19.4 kg of reaction solution (1-1) and 19.4 kg of diphenyl carbonate from Example 1-1, reaction solution (1-1) was fed into the reactor over approximately 13 minutes to initiate the reaction. The reaction was carried out within a range of 248°C jacket temperature, 240°C internal temperature, reflux ratio, and pressure from 14 to 26 kPa. After all of reaction solution (1-1) was transferred, phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of reaction solution transferred to storage tank 205 was 20.96 kg. The reaction solution (hereinafter referred to as "reaction solution (2-2)") was analyzed by NMR, LC, and gas chromatography, and TTI was produced in a yield of 78% by mass. At this point, the value of the reaction solution {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of ureaketimide group)+2×(molar amount of ureacarbate group)}÷(molar amount of carbonyl compound) is 4.3.

[0615] Process (2-3): Light-boil separation process

[0616] The reaction solution (2-2) was continuously fed at a rate of 4.19 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.26 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 6.29 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TTI was recovered in a yield of 77% by mass relative to the supplied reaction solution (2-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 6.3.

[0617] Process (2-4): High-boiling point separation process

[0618] Except for the liquid recovered into storage tank 303 in steps (2-3), high-boiling separation was performed using the same procedure as in Example 1-1. 3.36 kg of liquid was recovered into storage tank 402, representing a TTI recovery rate of 116% by mass.

[0619] [Examples 1-3]

[0620] Process (3-2): Thermal decomposition process of carbamate compounds

[0621] Using 19.4 kg of reaction solution (1-1) and 19.4 kg of diphenyl carbonate from Example 1-1, reaction solution (1-1) was fed into the reactor over approximately 9 minutes to initiate the reaction. The reaction was carried out within a range of 258°C jacket temperature, 250°C internal temperature, reflux ratio 2.0, and pressure 21 to 32 kPa. After all of reaction solution (1-1) was transferred, the phenol was discharged for an additional 2.5 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 22.12 kg. The reaction solution (hereinafter referred to as "reaction solution (3-2)") was analyzed by NMR, LC, and gas chromatography, and the results showed that TTI was produced in a yield of 73% by mass. At this point, the value of the reaction solution {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of ureaketimide group)+2×(molar amount of ureacarbate group)}÷(molar amount of carbonyl compound) is 3.9.

[0622] Process (3-3): Light-boil separation process

[0623] The reaction solution (3-2) was continuously fed at a rate of 4.42 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.42 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 7.08 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TTI was recovered at a yield of 80% by mass relative to the supplied reaction solution (3-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 5.5.

[0624] Process (3-4): High-boiling point separation process

[0625] Except for the liquid recovered into storage tank 303 in step (3-3), high-boiling separation was performed by the same procedure as in Example 1-1. 3.35 kg of liquid was recovered into storage tank 402, and the TTI recovery rate was 119% by mass.

[0626] [Examples 1-4]

[0627] Process (4-2): Thermal decomposition process of carbamate compounds

[0628] Using 19.4 kg of reaction solution (1-1) and 19.4 kg of diphenyl carbonate from Example 1-1, reaction solution (1-1) was fed into the reactor over approximately 14 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 1.5, and pressure 8 to 14 kPa. After all of reaction solution (1-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The weight of the reaction solution transferred to storage tank 205 was 22.12 kg. The reaction solution (hereinafter referred to as "reaction solution (4-2)") was analyzed by NMR, LC, and gas chromatography, and the results showed that TTI was produced in a yield of 79% by mass. At this point, the value of the reaction solution {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of ureaketimide group)+2×(molar amount of ureacarbate group)}÷(molar amount of carbonyl compound) is 1.6.

[0629] Process (4-3): Light-boil separation process

[0630] The reaction solution (4-2) was continuously fed at a rate of 4.42 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.68 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 8.41 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TTI was recovered in 85% by mass relative to the supplied reaction solution (4-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.6.

[0631] Process (4-4): High-boiling-point separation process

[0632] Except for the liquid recovered into storage tank 303 in step (4-3), high-boiling separation was performed using the same procedure as in Example 1-1. 4.05 kg of liquid was recovered into storage tank 402, and the TTI recovery rate was 125% by mass.

[0633] [Examples 1-5]

[0634] Process (5-1): Manufacturing process of carbamate compounds

[0635] Urea 0.23 kg (69.2 mol) was used instead of diphenyl carbonate, so that 25.87 kg (275.2 mol) of phenol was supplied to storage tank 102. The reaction temperature in reactor 104 was set to 240°C, and the mixture was stirred for 30 minutes. Otherwise, the urethane was synthesized by the same procedure as in Example 1-1. The amount of phenol and ammonia discharged into storage tank 107 was 24.14 kg.

[0636] The solution after the reaction (hereinafter referred to as "reaction solution (5-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was generated in 99% by mass. The reaction solution (5-1) was then transferred to storage tank 106 via open line 16. The mass of reaction solution (5-1) was 10.79 kg.

[0637] Process (5-2): Thermal decomposition process of carbamate compounds

[0638] Using 10.8 kg of reaction solution (5-1) from Example 1-1 and 28.0 kg of diphenyl carbonate, reaction solution (5-1) was fed into the reactor over approximately 13 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 1.7, and pressure 8 to 14 kPa. After all of reaction solution (5-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 21.34 kg. The reaction solution (hereinafter referred to as "reaction solution (5-2)") was analyzed by NMR, LC, and gas chromatography, and the results showed that TTI was produced in a yield of 78% by mass. At this point, the value of the reaction solution {3×(molar amount of isocyanurate group)+2×(molar amount of carbodiimide group)+3×(molar amount of urea ketimide group)+2×(molar amount of urea carbamate group)}÷(molar amount of carbonyl compound) is 1.5.

[0639] Process (5-3): Light-boil separation process

[0640] The reaction solution (5-2) was continuously fed at a rate of 4.27 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.75 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 8.75 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TTI was recovered in 84% by mass relative to the supplied reaction solution (5-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.5.

[0641] Process (5-4): High-boiling-point separation process

[0642] Except for the liquid recovered in storage tank 303 in step (5-3), high-boiling separation was performed by the same procedure as in Example 1-1. 4.05 kg of liquid was recovered in storage tank 402, and the TTI recovery rate was 128% by mass.

[0643] [Examples 1-6]

[0644] Process (6-1): Manufacturing process of carbamate compounds

[0645] 12.40 kg (58.5 mol) of 4-cumylphenol was fed into SUS reactor 104 with baffles instead of phenol, and 18.97 kg (89.47 mol) of 4-cumylphenol was fed into SUS reactor 105 with baffles instead of phenol. The urethane synthesis was otherwise carried out by the same procedure as in Examples 1-5. 16.97 kg of 4-cumylphenol and ammonia were discharged into storage tank 107.

[0646] The solution after the reaction (hereinafter referred to as "reaction solution (6-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was generated in 99% by mass. The reaction solution (6-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (6-1) was 17.96 kg.

[0647] Process (6-2): Thermal decomposition process of carbamate compounds

[0648] Using 18.0 kg of reaction solution (6-1) and 28.0 kg of bis(4-cumylphenyl) carbonate, reaction solution (6-1) was fed into the reactor over approximately 12 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 1.5, and pressure 3 to 5 kPa. After all of reaction solution (6-1) was transferred, the 4-cumylphenol was discharged over another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Examples 1-5. The mass of the reaction solution transferred to storage tank 205 was 32.19 kg. The reaction solution (hereinafter referred to as "reaction solution (6-2)") was analyzed by NMR, LC, and gas chromatography, and TTI was produced in a yield of 75% by mass. At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compound) is 1.4. A portion of the reaction solution (6-2) is purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is a mixture of compounds represented by the following formulas (I-3a) to (I-3c).

[0649] [Chemistry 70]

[0650]

[0651] Process (6-3): Light-boil separation process

[0652] The reaction solution (6-2) was continuously fed at a rate of 16.10 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 15.77 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 31.55 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TTI was recovered in 95% by mass relative to the supplied reaction solution (6-2). At this point, the value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 1.6.

[0653] Process (6-4): High-boiling-point separation process

[0654] Except for the liquid recovered into storage tank 303 in step (6-3), high-boiling separation was performed by the same procedure as in Example 1-1. 4.19 kg of liquid was recovered into storage tank 402, representing a TTI recovery rate of 122% by mass.

[0655] [Comparative Example 1-1]

[0656] Process (1'-2): Thermal decomposition process of carbamate compounds

[0657] Using 19.4 kg of reaction solution (1-1) from Example 1-1 and 5.45 kg of Barrel Process Oil B-03 (benzyltoluene, Matsumura Oil Co., Ltd.), reaction solution (1-1) was fed into the reactor over approximately 14 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 1.5, and pressure 25 to 35 kPa. After all of reaction solution (1-1) was transferred, phenol was discharged for an additional 1.5 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of reaction solution transferred to storage tank 205 was 5.71 kg. The reaction solution (hereinafter referred to as "reaction solution (1'-2)") was analyzed by NMR, LC, and gas chromatography, and TTI was produced in a yield of 69% by mass. At this point, no carbonyl compounds were observed to form in the reaction solution, but byproducts with isocyanurate, carbodiimide, urea-ketimide, and urea-formate groups were observed.

[0658] Process (1'-3): Light-boil separation process

[0659] The reaction solution (1'-2) was continuously fed at 4.35 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.74 kg / h. In addition, light boiling separation was performed by the same operation as in Example 1-1. As a result, the liquid became highly viscous during operation, making it difficult to continue operation.

[0660] [Examples 1-7]

[0661] Process (7-1): Manufacturing process of carbamate compounds

[0662] use Figure 1 The apparatus shown undergoes the reaction.

[0663] With pipeline 14 closed, 3.33 kg (16.8 mol) of 4,4'-diaminodiphenylmethane is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.53 kg (27.0 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 2.53 kg (27.0 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.96 kg (55.6 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, a mixture of 4,4'-diaminodiphenylmethane and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 7.58 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0664] The resulting solution (hereinafter referred to as "reaction solution (7-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4,4'-diaminodiphenylmethane was produced in 95% by mass. The reaction solution (7-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (7-1) was 12.77 kg.

[0665] Process (7-2): Thermal decomposition process of carbamate compounds

[0666] Using 12.77 kg of reaction solution (7-1) and 12.77 kg of diphenyl carbonate, reaction solution (7-1) was fed into the reactor over approximately 10 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio, and pressure of 11 to 16 kPa. After all of reaction solution (7-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 11.75 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (7-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-2).

[0667] [Chemistry 71]

[0668]

[0669] LC calibration curves were prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified using the absolute calibration curve method. Analysis was performed by NMR and gas chromatography, revealing a yield of diphenylmethane diisocyanate (MDI) of 70% by mass. The value of the reaction solution at this point, {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urea-formate groups)} ÷ (molar amount of carbonyl compound), was 1.3.

[0670] Process (7-3): Light-boil separation process

[0671] The reaction solution (7-2) was continuously fed at a rate of 2.35 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.97 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 9.87 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that MDI was recovered in 79% by mass relative to the supplied reaction solution (7-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.3.

[0672] Process (7-4): High-boiling-point separation process

[0673] Using the liquid recovered in storage tank 303 in step (7-3), the operating temperature was set to 170°C and the internal pressure to 0.3 kPa, otherwise high-boiling separation was performed using the same procedures as in Example 1-1. 4.54 kg of liquid was recovered into storage tank 402, and the MDI recovery rate was 130% by mass.

[0674] [Examples 1-8]

[0675] Process (8-1): Manufacturing process of carbamate compounds

[0676] With pipeline 14 closed, 3.33 kg (16.8 mol) of lysine β-aminoethyl ester trihydrochloride is supplied from storage tank 101 via pipeline 11 to an SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.52 kg (26.7 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104. The mixture is stirred to achieve homogenization. Next, with pipeline 16 closed, 2.52 kg (26.7 mol) of phenol is supplied from storage tank 102 via pipeline 15 to an SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.91 kg (55.6 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, a mixture of lysine β-aminoethyl ester trihydrochloride and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 8.22 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0677] The resulting solution (hereinafter referred to as "reaction solution (8-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to lysine β-aminoethyl ester was generated in 96% by mass. The reaction solution (8-1) was then transferred to storage tank 106 via open line 16. The mass of reaction solution (8-1) was 11.45 kg.

[0678] Process (8-2): Thermal decomposition process of carbamate compounds

[0679] Using 11.45 kg of reaction solution (8-1) and 10.00 kg of diphenyl carbonate, reaction solution (8-1) was fed into the reactor over approximately 15 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 3.2, and pressure 11 to 16 kPa. After all of reaction solution (8-1) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution (hereinafter referred to as "reaction solution (8-2)") transferred to storage tank 205 was 9.01 kg. The reaction solution (8-2) was... 1 The results of H-NMR and gas chromatography-mass spectrometry are shown in the figures below. Figure 6Aand Figure 6B In addition, a portion of the reaction solution (8-2) was purified using a column fractionation apparatus, thereby separating the carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-4a) to (I-4c).

[0680] [Chemistry 72]

[0681]

[0682] LC calibration curves were prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified using the absolute calibration curve method. Analysis was performed by NMR and gas chromatography, revealing the formation of lysine triisocyanate (LTI) in 77% by mass. The value of the reaction solution at this point, {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urea-formate groups)} ÷ (molar amount of carbonyl compound), was 1.4.

[0683] Process (8-3): Light-boil separation process

[0684] The reaction solution (8-2) was continuously fed at a rate of 1.80 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.10 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 5.50 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that LTI was recovered at a yield of 83% by mass relative to the supplied reaction solution (8-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.4.

[0685] Process (8-4): High-boiling-point separation process

[0686] Using the liquid recovered in storage tank 303 in step (8-3), the operating temperature was set to 190°C and the internal pressure to 0.1 kPa, otherwise high-boiling separation was performed using the same procedure as in Example 1-1. 2.38 kg of liquid was recovered into storage tank 402, representing a LTI recovery rate of 125% by mass.

[0687] [Examples 1-9]

[0688] Process (9-1): Manufacturing process of carbamate compounds

[0689] 0.84 kg (6.75 mol) of 2-methoxyphenol was fed into SUS reactor 104 with baffles instead of phenol, and 0.84 kg (6.75 mol) of 2-methoxyphenol and 15.26 kg (55.6 mol) of bis(2-methoxyphenyl) carbonate were fed into SUS reactor 105 with baffles instead of phenol. The urethane synthesis was otherwise carried out by the same procedure as in Examples 1-8. 6.35 kg of 2-methoxyphenol was discharged into storage tank 107.

[0690] The resulting solution (hereinafter referred to as "reaction solution (9-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was produced in 98% by mass. The reaction solution (9-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (9-1) was 13.95 kg.

[0691] Process (9-2): Thermal decomposition process of carbamate compounds

[0692] Using 14.0 kg of reaction solution (9-1) and 8.0 kg of bis(2-methoxyphenyl) carbonate, reaction solution (9-1) was fed into the reactor over approximately 14 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 3.0, and pressure 8 to 13 kPa. After all of reaction solution (9-1) was transferred, the reaction continued for 3 hours to remove 2-methoxyphenol. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Examples 1-8. The mass of reaction solution transferred to storage tank 205 was 12.05 kg. The reaction solution (hereinafter referred to as "reaction solution (9-2)") was analyzed by NMR, LC, and gas chromatography, and the results showed that LTI was produced in a yield of 78% by mass. At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compound) is 1.5. A portion of the reaction solution (9-2) is purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is a mixture of compounds represented by the following formulas (I-5a) to (I-5c).

[0693] [Chemistry 73]

[0694]

[0695] Process (9-3): Light-boil separation process

[0696] The reaction solution (9-2) was continuously fed at a pressure of 1.0 kPa at a rate of 2.41 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.16 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 5.79 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography showed that LTI was recovered in 85% by mass relative to the supplied reaction solution (9-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.2.

[0697] Process (9-4): High-boiling-point separation process

[0698] Except for the liquid recovered into storage tank 303 in process (9-3), high-boiling separation was performed by the same procedure as in Example 1-1. 2.43 kg of liquid was recovered into storage tank 402, representing a LTI recovery rate of 123% by mass.

[0699] [Examples 1-10]

[0700] Process (10-1): Manufacturing process of carbamate compounds

[0701] With pipeline 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride is supplied from storage tank 101 via pipeline 11 to an SUS-made reaction vessel 104 equipped with a flow guide plate, and 1.91 kg (20.3 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104. The mixture is stirred to achieve homogenization. Next, with pipeline 16 closed, 1.91 kg (20.3 mol) of phenol is supplied from storage tank 102 via pipeline 15 to an SUS-made reaction vessel 105 equipped with a flow guide plate, and 10.17 kg (47.5 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, the mixture of lysine methyl ester dihydrochloride and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 5.93 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0702] The resulting solution (hereinafter referred to as "reaction solution (10-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to lysine methyl ester was generated in 97% by mass. The reaction solution (10-1) was then transferred through line 16 to storage tank 106. The mass of the reaction solution (10-1) was 11.38 kg.

[0703] Process (10-2): Thermal decomposition process of carbamate compounds

[0704] Using 11.38 kg of reaction solution (10-1) and 11.38 kg of diphenyl carbonate, reaction solution (10-1) was fed into the reactor over approximately 12 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio, and pressure of 20 to 29 kPa. After all of reaction solution (10-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 19.35 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (10-2)") was purified using a column fractionation apparatus to separate carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-7a) to (I-7b).

[0705] [Chemistry 74]

[0706]

[0707] LC calibration curves were prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified using the absolute calibration curve method. Analysis was performed by NMR and gas chromatography, revealing that lysine diisocyanate (LDI) was generated in 81% by mass. The value of the reaction solution at this point, {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urea-formate groups)} ÷ (molar amount of carbonyl compound), was 1.4.

[0708] Process (10-3): Light-boil separation process

[0709] The reaction solution (10⁻²) was continuously fed at 3.87 kg / h, and the discharge rate of line 34 under steady-state conditions was 1.47 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 7.35 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that LDI was recovered in 86% by mass relative to the supplied reaction solution (10⁻²). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.5.

[0710] Process (10-4): High-boiling-point separation process

[0711] Using the liquid recovered from storage tank 303 in step (10-3), the operating temperature was set to 180°C and the internal pressure to 0.1 kPa, otherwise high-boiling separation was performed using the same procedures as in Example 1-1. 4.57 kg of liquid was recovered into storage tank 402, and the LDI recovery rate was 122% by mass.

[0712] [Examples 1-11]

[0713] Process (11-1): Manufacturing process of carbamate compounds

[0714] 3.33 kg (13.5 mol) of lysine ethyl dihydrochloride (replacing lysine methyl dihydrochloride) and 1.70 kg (18.04 mol) of phenol were fed into an SUS reactor 104 equipped with a baffle plate. 1.70 kg (18.04 mol) of phenol and 9.59 kg (44.81 mol) of diphenyl carbonate were fed into an SUS reactor 105 equipped with a baffle plate. The urethane synthesis was otherwise carried out using the same procedures as in Examples 1-10. 5.59 kg of phenol was discharged into storage tank 107.

[0715] The resulting solution (hereinafter referred to as "reaction solution (11-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was produced in 97% by mass. The reaction solution (11-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (11-1) was 10.74 kg.

[0716] Process (11-2): Thermal decomposition process of carbamate compounds

[0717] Using 10.7 kg of reaction solution (11-1) and 10.74 kg of diphenyl carbonate, reaction solution (11-1) was fed into the reactor over approximately 12 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio, and pressure of 20 to 29 kPa. After all of reaction solution (11-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Examples 1-10. The mass of the reaction solution transferred to storage tank 205 was 18.25 kg. The reaction solution (hereinafter referred to as "reaction solution (11-2)") was analyzed by NMR, LC, and gas chromatography, and the results showed that LDI-Et was produced in a yield of 82% by mass. At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compound) is 1.3. A portion of the reaction solution (11-2) is purified using a column fractionation apparatus, thereby separating the carbonyl compound. The separated carbonyl compound is a mixture of compounds represented by the following formulas (I-10a) to (I-10b).

[0718] [Chemistry 75]

[0719]

[0720] Process (11-3): Light-boil separation process

[0721] The reaction solution (11-2) was continuously fed at 3.65 kg / h, and the discharge rate of pipeline 34 under steady-state conditions was 1.31 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 6.57 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography showed that LDI-Et was recovered in 85% by mass relative to the supplied reaction solution (11-2). At this point, the value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 2.2.

[0722] Process (11-4): High-boiling-point separation process

[0723] Except for the liquid recovered in storage tank 303 in process (11-3), high-boiling separation was performed by the same procedure as in Example 1-1. 4.10 kg of liquid was recovered in storage tank 402, and the LDI-Et recovery rate was 120% by mass.

[0724] [Examples 1-12]

[0725] Process (12-1): Manufacturing process of carbamate compounds

[0726] With pipeline 14 closed, 3.33 kg (15.8 mol) of 4,4'-methylenebis(cyclohexylamine) is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.29 kg (24.4 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 2.29 kg (24.4 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.27 kg (52.7 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the solution, a mixture of 4,4'-methylenebis(cyclohexylamine) and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction solution is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 6.94 kg of phenol is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0727] The resulting solution (hereinafter referred to as "reaction solution (12-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4,4'-methylenebis(cyclohexylamine) was produced in 99% by mass. The reaction solution (12-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (12-1) was 12.24 kg.

[0728] Process (12-2): Thermal decomposition process of carbamate compounds

[0729] Using 12.24 kg of reaction solution (12-1) and 12.24 kg of diphenyl carbonate, reaction solution (12-1) was fed into the reactor over approximately 10 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.5, and pressure 11 to 16 kPa. After all of reaction solution (12-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 9.79 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (12-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-16).

[0730] [Chemistry 76]

[0731]

[0732] LC calibration curves were prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified using the absolute calibration curve method. Analysis was performed by NMR, LC, and gas chromatography, revealing a yield of methylene bis(cyclohexyl isocyanate) (HMDI) of 76% by mass. The value of the reaction solution at this point, {3×(molar amount of isocyanurate groups) + 2×(molar amount of carbodiimide groups) + 3×(molar amount of urea-ketimide groups) + 2×(molar amount of urea-formate groups)} ÷ (molar amount of carbonyl compound), was 2.0.

[0733] Process (12-3): Light-boil separation process

[0734] The reaction solution (12-2) was continuously fed at a rate of 1.96 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.65 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 8.22 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that HMDI was recovered in 82% by mass relative to the supplied reaction solution (12-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 3.4.

[0735] Process (12-4): High-boiling-point separation process

[0736] Using the liquid recovered from storage tank 303 in process (12-3), the operating temperature was set to 190°C and the internal pressure to 0.3 kPa, otherwise high-boiling separation was performed using the same procedures as in Example 1-1. 4.85 kg of liquid was recovered into storage tank 402, and the HMDI recovery rate was 125% by mass.

[0737] [Examples 1-13]

[0738] Process (13-1): Manufacturing process of carbamate compounds

[0739] With pipeline 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 4.11 kg (43.7 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Then, with pipeline 16 closed, 4.11 kg (43.7 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 16.44 kg (76.8 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the mixture, a mixture of 1,3-di(aminomethyl)cyclohexane and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 11.74 kg of phenol in the liquid is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0740] The resulting solution (hereinafter referred to as "reaction solution (13-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane was produced in 99% by mass. The reaction solution (13-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (13-1) was 16.24 kg.

[0741] Process (13-2): Thermal decomposition process of carbamate compounds

[0742] Using 16.24 kg of reaction solution (13-1) and 16.24 kg of diphenyl carbonate, reaction solution (13-1) was fed into the reactor over approximately 15 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.0, and pressure 11 to 16 kPa. After all of reaction solution (13-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 13.97 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (13-2)") was purified using a column fractionation apparatus to separate carbonyl compounds. The separated carbonyl compounds are those represented by the following formula (I-19).

[0743] [Chemistry 77]

[0744]

[0745] LC calibration curves were prepared from the obtained carbonyl compounds, and the carbonyl compounds were quantified using the absolute calibration curve method. Analysis was performed by NMR, LC, and gas chromatography, revealing the formation of 1,3-bis(isocyanate methyl)cyclohexane (HXDI) in 78% by mass. The value of {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urea-formate groups)} ÷ (molar amount of carbonyl compound) was 1.7.

[0746] Process (13-3): Light-boil separation process

[0747] The reaction solution (13-2) was continuously fed at a rate of 2.79 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.90 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Example 1-1. 9.50 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that HXDI was recovered in 77% by mass relative to the supplied reaction solution (13-2). At this point, the value of the reaction solution {3 × (molar amount of isocyanurate groups) + 2 × (molar amount of carbodiimide groups) + 3 × (molar amount of urea-ketimide groups) + 2 × (molar amount of urethane groups)} ÷ (molar amount of carbonyl compounds) was 3.6.

[0748] Process (13-4): High-boiling-point separation process

[0749] Using the liquid recovered from storage tank 303 in step (13-3), the operating temperature was set to 190°C and the internal pressure to 0.3 kPa, except that high-boiling separation was performed using the same procedures as in Example 1-1. 4.93 kg of liquid was recovered into storage tank 402, and the HXDI recovery rate was 122% by mass.

[0750] <Preparation of isocyanate compounds and corresponding carbonyl compounds (I)>

[0751] [Synthesis Example 1-1]

[0752] (Preparation of TTI and its corresponding carbonyl compounds (I-1a) to (I-1c))

[0753] 1. Process (1-1): Manufacturing process of carbamate compounds

[0754] use Figure 1 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the preparation of the carbamate compounds following Synthetic Example 1-1. Figure 1 The apparatus shown.

[0755] With pipeline 14 closed, 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 5.50 kg (58.5 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 5.50 kg (58.5 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reactor 105 equipped with a flow guide plate, and 20.52 kg (95.9 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the solution, a mixture of 4-aminomethyl-1,8-octanediamine and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction solution is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 15.53 kg of phenol is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0756] The resulting solution (hereinafter referred to as "reaction solution (1-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was produced in 99% by mass. The reaction solution (1-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (1-1) was 19.40 kg.

[0757] 2. Process (1-2): Thermal decomposition process of carbamate compounds

[0758] use Figure 2 The apparatus shown is used for the reaction. It should be noted that this apparatus is also used in the thermal decomposition of the carbamate compound following Synthesis Example 1-1. Figure 2 The apparatus shown.

[0759] With pipeline 24 closed, 19.40 kg of diphenyl carbonate is supplied from storage tank 202 to SUS reaction vessel 201 with baffles via pipeline 22. The temperature of multistage distillation column 203 is raised to 170°C, the jacket temperature of reaction vessel 201 is heated to 228°C, and the pressure is reduced to 14 kPa. 19.40 kg of reaction liquid (1-1) recovered from storage tank 106 in step (1-1) is heated to 120°C and supplied to reaction vessel 201 via pipeline 21 over approximately 15 minutes for thermal decomposition of the carbamate compound. The pressure is adjusted to a range of 8 to 14 kPa, and the phenol generated by thermal decomposition is separated from diphenyl carbonate and the product 1,8-diisocyanate-4-isocyanate-methyloctane (TTI) via distillation column 203, and recovered to storage tank 204 via pipeline 25, condenser A21, and pipeline 27. The reflux ratio at this point is 1.2. After all of the reaction solution (1-1) has been transferred, the phenol discharge is further carried out at an internal temperature of 220°C. Four hours after all of the reaction solution (1-1) has been transferred, the reaction is terminated, and the reaction solution is discharged from pipeline 28 and transferred to storage tank 205. The mass of the reaction solution transferred to storage tank 205 is 18.63 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (1-2)") is purified using a column fractionation device to separate the carbonyl compounds. The separated carbonyl compounds are a mixture of compounds represented by the following formulas (I-1a) to (I-1c) (hereinafter, this mixture is sometimes referred to as "mixture (I-1)"). And proceed with... 1 H-NMR and gas chromatography analyses showed that TTI was produced in a yield of 70% by mass.

[0760] [Chemistry 78]

[0761]

[0762] 3. Process (1-3): Light-boil separation process

[0763] use Figure 3 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the light-boiling separation following Synthesis Example 1-1. Figure 3 The apparatus shown.

[0764] The reaction solution (1-2) is continuously fed from storage tank 205 through pipeline 31 at a rate of 3.73 kg / h to the middle section of continuous multistage distillation column 301 for distillation separation of the liquid phase components. The liquid at the bottom of the column is circulated through reboiler A32 and pipeline 33, thereby supplying the heat required for distillation separation. The liquid temperature at the bottom of the continuous multistage distillation column is 220°C, and the pressure at the top of the column is 1.5 kPa. The gas distilled from the top of the continuous multistage distillation column 301 is condensed by condenser A31 through pipeline 32 and continuously discharged into storage tank 302 through pipeline 36. In addition, the gas is continuously discharged into storage tank 303 at a steady-state discharge rate of 1.49 kg / h through pipeline 34. The amount of liquid recovered into storage tank 303 (hereinafter referred to as "reaction liquid (1-3)") was 7.45 kg. The analysis by NMR, LC and gas chromatography showed that TTI was recovered in a yield of 82% by mass relative to the supplied reaction liquid (1-2).

[0765] 4. Process (1-4): High-boiling-point separation process

[0766] use Figure 4 The apparatus shown is used for the reaction. It should be noted that the apparatus is also used in the high-boiling separation following Synthesis Example 1-1. Figure 4 The apparatus shown.

[0767] The thin-film distillation apparatus 401 (manufactured by KOBELCO ECO-SOLUTIONS, Japan) is heated to 190°C, and the internal pressure is set to 0.3 kPa. The reaction liquid (1-3) recovered from the storage tank 303 in steps (1-3) is supplied to the upper part of the thin-film distillation apparatus 401 via pipeline 41 at approximately 1.0 kg / hour for separation of isocyanate and high-boiling components. The generated gaseous components are transported to the storage tank 402 via pipeline 42 and condenser A41. The liquid recovered from the storage tank 402 is 3.35 kg, and the TTI recovery rate is 121% by mass. It should be noted that the reason why the TTI recovery rate exceeds 100% by mass is that a portion of the isocyanate modified product generated in the thermal decomposition step or the light-boiling separation step is regenerated as TTI.

[0768] [Synthesis example 1-2]

[0769] (Preparation of TTI and its corresponding carbonyl compounds (I-2a) to (I-2c))

[0770] In Synthesis Example 1-1, 2-methoxyphenol was used instead of phenol, and bis(2-methoxyphenyl) carbonate was used instead of diphenyl carbonate. Otherwise, TTI was prepared using the same method as in Synthesis Example 1-1. In this case, the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-2a) to (I-2c) (hereinafter, this mixture is sometimes referred to as "mixture (I-2)").

[0771] [Chemistry 79]

[0772]

[0773] [Synthesis Example 1-3]

[0774] (Preparation of TTI and its corresponding carbonyl compounds (I-3a) to (I-3c))

[0775] In Synthesis Example 1-1, 4-cumylphenol was used instead of phenol, and bis(4-cumylphenol) carbonate was used instead of diphenyl carbonate. Otherwise, TTI was prepared using the same method as in Synthesis Example 1-1. In this case, the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-3a) to (I-3c) (hereinafter, this mixture is sometimes referred to as "mixture (I-3)").

[0776] [Chemistry 80]

[0777]

[0778] [Synthesis Example 1-4]

[0779] (Preparation of LTI and its corresponding carbonyl compounds (I-4a) to (I-4b))

[0780] 1. Process (4-1): Manufacturing process of carbamate compounds

[0781] With pipeline 14 closed, 3.33 kg (16.8 mol) of lysine β-aminoethyl ester trihydrochloride is supplied from storage tank 101 via pipeline 11 to an SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.52 kg (26.7 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104. The mixture is stirred to achieve homogenization. Next, with pipeline 16 closed, 2.52 kg (26.7 mol) of phenol is supplied from storage tank 102 via pipeline 15 to an SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.91 kg (55.6 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, a mixture of lysine β-aminoethyl ester trihydrochloride and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 8.22 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0782] The resulting solution (hereinafter referred to as "reaction solution (4-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to lysine β-aminoethyl ester was generated in 96% by mass. The reaction solution (4-1) was then transferred to storage tank 106 via open line 16. The mass of reaction solution (4-1) was 11.45 kg.

[0783] 2. Process (4-2): Thermal decomposition process of carbamate compounds

[0784] Using 11.45 kg of reaction solution (4-1) and 10.00 kg of diphenyl carbonate, reaction solution (4-1) was fed into the reactor over approximately 15 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 3.2, and pressure 11 to 16 kPa. After all of reaction solution (4-1) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 9.01 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (4-2)") was purified using a column fractionation apparatus to separate the carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-4a) to (I-4c) (hereinafter, this mixture is sometimes referred to as "mixture (I-4)"). Analysis by NMR and gas chromatography revealed that lysine triisocyanate (LTI) was produced in a yield of 77% by mass.

[0785] [Chemistry 81]

[0786]

[0787] 3. Process (4-3): Light-boiling separation process

[0788] The reaction solution (4-2) was continuously fed at a rate of 1.80 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.10 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 5.50 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that LTI was recovered in 83% by mass relative to the supplied reaction solution (4-2).

[0789] 4. Process (4-4): High-boiling-point separation process

[0790] Using the liquid recovered in storage tank 303 in step (4-3), the operating temperature was set to 190°C and the internal pressure to 0.1 kPa, otherwise high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 2.38 kg of liquid was recovered into storage tank 402, representing a LTI recovery rate of 125% by mass.

[0791] [Synthesis Example 1-5]

[0792] (Preparation of LTI and its corresponding carbonyl compounds (I-5a) to (I-5b))

[0793] In Synthetic Examples 1-4, 2-methoxyphenol was used instead of phenol, and bis(2-methoxyphenyl) carbonate was used instead of diphenyl carbonate. Otherwise, LTI was prepared using the same method as in Synthetic Examples 1-4. In this case, the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-5a) to (I-5c) (hereinafter, this mixture is sometimes referred to as "mixture (I-5)").

[0794] [Chemistry 82]

[0795]

[0796] [Synthesis Example 1-6]

[0797] (Preparation of LDI and its corresponding carbonyl compounds (I-7a) to (I-7b))

[0798] 1. Process (6-1): Manufacturing process of carbamate compounds

[0799] With pipeline 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride is supplied from storage tank 101 via pipeline 11 to an SUS-made reaction vessel 104 equipped with a flow guide plate, and 1.91 kg (20.3 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104. The mixture is stirred to achieve homogenization. Next, with pipeline 16 closed, 1.91 kg (20.3 mol) of phenol is supplied from storage tank 102 via pipeline 15 to an SUS-made reaction vessel 105 equipped with a flow guide plate, and 10.17 kg (47.5 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, the mixture of lysine methyl ester dihydrochloride and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 5.93 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0800] The resulting solution (hereinafter referred to as "reaction solution (6-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to lysine methyl ester was generated in 97% by mass. The reaction solution (6-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (6-1) was 11.38 kg.

[0801] 2. Process (6-2): Thermal decomposition process of carbamate compounds

[0802] Using 11.38 kg of reaction solution (6-1) and 11.38 kg of diphenyl carbonate, reaction solution (6-1) was fed into the reactor over approximately 12 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio of 0.9, and pressure of 20 to 29 kPa. After all of reaction solution (6-1) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 19.35 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (6-2)") was purified using a column fractionation apparatus to separate the carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-7a) to (I-7b) (hereinafter, this mixture is sometimes referred to as "mixture (I-7)"). Furthermore, analysis by NMR and gas chromatography revealed that lysine diisocyanate (LDI) was generated in a yield of 81% by mass.

[0803] [Chemistry 83]

[0804]

[0805] 3. Process (6-3): Light-boiling separation process

[0806] The reaction solution (6-2) was continuously fed at a rate of 3.87 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.47 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 7.35 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that LDI was recovered in 86% by mass relative to the supplied reaction solution (6-2).

[0807] 4. Process (6-4): High-boiling-point separation process

[0808] Using the liquid recovered from storage tank 303 in step (6-3), the operating temperature was set to 180°C and the internal pressure to 0.1 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.57 kg of liquid was recovered from storage tank 402, resulting in a LDI recovery rate of 122% by mass.

[0809] [Synthesis Example 1-7]

[0810] (Preparation of LDI and its corresponding carbonyl compounds (I-8a) to (I-8b))

[0811] In Synthetic Examples 1-6, 2-methoxyphenol was used instead of phenol, and bis(2-methoxyphenyl) carbonate was used instead of diphenyl carbonate. Otherwise, LDI was produced using the same method as in Synthetic Examples 1-6. In this case, the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-8a) to (I-8b) (hereinafter, this mixture is sometimes referred to as "mixture (I-8)").

[0812] [Chemistry 84]

[0813]

[0814] [Synthesis Example 1-8]

[0815] (Preparation of LDI-Et and the corresponding carbonyl compounds (I-10a) to (I-10b))

[0816] In Synthesis Examples 1-6, lysine ethyl ester dihydrochloride was used instead of lysine methyl ester dihydrochloride, and LDI-Et was otherwise manufactured using the same method as in Synthesis Examples 1-6. In this case, the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-10a) to (I-10b) (hereinafter, this mixture is sometimes referred to as "mixture (I-10)").

[0817] [Chemistry 85]

[0818]

[0819] [Synthesis Example 1-9]

[0820] (Preparation of HDI and its corresponding carbonyl compound (I-20))

[0821] 1. Process (9-1): Manufacturing process of carbamate compounds

[0822] Using 3.33 kg of hexamethylenediamine (as a substitute for 4-aminomethyl-1,8-octanediamine) and 20.40 kg of diphenyl carbonate, 5.50 kg of phenol was mixed with hexamethylenediamine and fed into the reactor. Otherwise, the corresponding carbamate was synthesized from hexamethylenediamine by the same method as in step (1-1). The reaction solution was heated to 120°C and the internal pressure was set to 1.0 kPa. 15.42 kg of phenol was discharged from the liquid.

[0823] The solution after the reaction (hereinafter referred to as "reaction solution (9-1)") was analyzed by liquid chromatography, and the carbamate compound corresponding to hexamethylenediamine was generated in 99% by mass. The mass of the above reaction solution (9-1) was 19.31 kg.

[0824] 2. Process (9-2): Thermal decomposition process of carbamate compounds

[0825] Using 19.31 kg of reaction solution (9-1) and 19.31 kg of diphenyl carbonate, reaction solution (9-1) was fed into the reactor over approximately 15 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 2.2, and pressure 20 to 29 kPa. After all of reaction solution (9-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution after the reaction (hereinafter referred to as "reaction solution (9-2)") was 33.22 kg. The carbonyl compound of reaction solution (9-2) was isolated. The isolated carbonyl compound is the compound represented by the following formula (I-20).

[0826] [Chemistry 86]

[0827]

[0828] In addition, analysis by NMR and gas chromatography showed that hexamethylene diisocyanate (HDI) was produced in a yield of 78% by mass.

[0829] 3. Process (9-3): Light-boil separation process

[0830] The reaction solution (9-2) was continuously fed at a rate of 6.64 kg / h, and the discharge rate from line 34 under steady-state conditions was 0.930 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.65 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that HDI was recovered in 83% by mass relative to the supplied reaction solution (9-2).

[0831] 4. Process (9-4): High-boiling-point separation process

[0832] Using the liquid recovered in storage tank 303 in step (9-3), the operating temperature was set to 170°C and the internal pressure to 0.1 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.55 kg of liquid was recovered into storage tank 402, and the HDI recovery rate was 122% by mass.

[0833] [Synthesis Example 1-10]

[0834] (Preparation of HMDI and its corresponding carbonyl compound (I-8))

[0835] 1. Process (10-1): Manufacturing process of carbamate compounds

[0836] With pipeline 14 closed, 3.33 kg (15.8 mol) of 4,4'-methylenebis(cyclohexylamine) is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.29 kg (24.4 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 2.29 kg (24.4 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.27 kg (52.7 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the solution, a mixture of 4,4'-methylenebis(cyclohexylamine) and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction solution is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 6.94 kg of phenol is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0837] The resulting solution (hereinafter referred to as "reaction solution (10-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4,4'-methylenebis(cyclohexylamine) was produced in 99% by mass. The reaction solution (10-1) was then transferred to storage tank 106 via open line 16. The mass of reaction solution (10-1) was 12.24 kg.

[0838] 2. Process (10-2): Thermal decomposition process of carbamate compounds

[0839] Using 12.24 kg of reaction solution (10-1) and 12.24 kg of diphenyl carbonate, reaction solution (10-1) was fed into the reactor over approximately 10 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.5, and pressure 11 to 16 kPa. After all of reaction solution (10-1) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 9.79 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (10-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-16).

[0840] [Chemistry 87]

[0841]

[0842] In addition, analysis by NMR, LC and gas chromatography showed that methylene bis(cyclohexyl isocyanate) (HMDI) was produced in a yield of 76% by mass.

[0843] 3. Process (10-3): Light-boiling separation process

[0844] The reaction solution (10⁻²) was continuously fed at a rate of 1.96 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.65 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 8.22 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that HMDI was recovered in 82% by mass relative to the supplied reaction solution (10⁻²).

[0845] 4. Process (10-4): High-boiling-point separation process

[0846] Using the liquid recovered from storage tank 303 in step (10-3), the operating temperature was set to 190°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.85 kg of liquid was recovered into storage tank 402, and the HMDI recovery rate was 125% by mass.

[0847] [Synthesis Example 1-11]

[0848] (Preparation of HXDI and its corresponding carbonyl compound (I-19))

[0849] 1. Process (11-1): Manufacturing process of carbamate compounds

[0850] With pipeline 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 4.11 kg (43.7 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Then, with pipeline 16 closed, 4.11 kg (43.7 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 16.44 kg (76.8 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to homogenize the mixture, a mixture of 1,3-di(aminomethyl)cyclohexane and phenol is supplied from reaction vessel 104 via pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, bringing the internal pressure to approximately 1 kPa. 11.74 kg of phenol in the liquid is then discharged into storage tank 107 via pipeline 17 and condenser A11.

[0851] The resulting solution (hereinafter referred to as "reaction solution (11-1)") was analyzed by liquid chromatography, yielding a carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane in 99% by mass. The reaction solution (11-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (11-1) was 16.24 kg.

[0852] 2. Process (11-2): Thermal decomposition process of carbamate compounds

[0853] Using 16.24 kg of reaction solution (11-1) and 16.24 kg of diphenyl carbonate, reaction solution (11-1) was fed into the reactor over approximately 15 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.0, and pressure 11 to 16 kPa. After all of reaction solution (11-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 13.97 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (11-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-19).

[0854] [Chemistry 88]

[0855]

[0856] In addition, analysis by NMR, LC and gas chromatography showed that 1,3-bis(isocyanate methyl)cyclohexane (HXDI) was produced in a yield of 78% by mass.

[0857] 3. Process (11-3): Light-boil separation process

[0858] The reaction solution (11-2) was continuously fed at a rate of 2.79 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.90 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 9.50 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that HXDI was recovered in 77% by mass relative to the supplied reaction solution (11-2).

[0859] 4. Process (11-4): High-boiling-point separation process

[0860] Using the liquid recovered from storage tank 303 in step (11-3), the operating temperature was set to 190°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.93 kg of liquid was recovered into storage tank 402, resulting in a HMDI recovery rate of 122% by mass.

[0861] [Synthesis Example 1-12]

[0862] (Preparation of PDI and its corresponding carbonyl compound (I-21))

[0863] 1. Process (12-1): Manufacturing process of carbamate compounds

[0864] Using 3.33 kg of 1,5-diaminopentane (instead of 4-aminomethyl-1,8-octanediamine) and 23.20 kg of diphenyl carbonate, 6.48 kg of phenol was mixed with 1,5-diaminopentane and fed into the reactor. Otherwise, the corresponding carbamate was synthesized from 1,5-diaminopentane using the same method as in the procedure (1-1) of Synthesis Example 1-1. The reaction solution was heated to 120°C and the internal pressure was set to 1.0 kPa, thereby removing 18.01 kg of phenol from the liquid.

[0865] The solution following the reaction (hereinafter referred to as "reaction solution (12-1)") was analyzed by liquid chromatography, and the carbamate compound corresponding to 1,5-diaminopentane was generated in 99% by mass. The amount of 1,5-diaminopentane in the above reaction solution (12-1) was 21.48 kg.

[0866] 2. Process (12-2): Thermal decomposition process of carbamate compounds

[0867] Using 21.48 kg of reaction solution (12-1) and 21.48 kg of diphenyl carbonate, reaction solution (12-1) was fed into the reactor over approximately 11 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.5, and pressure 20 to 29 kPa. After all of reaction solution (12-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution after the reaction was 37.38 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (12-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-21).

[0868] [Chemistry 89]

[0869]

[0870] In addition, analysis by NMR and gas chromatography showed that pentamethylene diisocyanate (PDI) was generated in a yield of 71% by mass.

[0871] 3. Process (12-3): Light-boiling separation process

[0872] The reaction solution (12-2) was continuously fed at 7.48 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.20 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 5.98 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that PDI was recovered in 87% by mass relative to the supplied reaction solution (12-2).

[0873] 4. Process (12-4): High-boiling-point separation process

[0874] Using the liquid recovered from storage tank 303 in step (12-3), the operating temperature was set to 160°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedures as in Synthesis Example 1-1. 3.53 kg of liquid was recovered into storage tank 402, and the PDI recovery rate was 115%.

[0875] [Synthesis Example 1-13]

[0876] (Preparation of IPDI and its corresponding carbonyl compounds (I-22a) to (I-22b))

[0877] 1. Process (13-1): Manufacturing process of carbamate compounds

[0878] Using 3.33 kg of isophorone diamine (instead of 4-aminomethyl-1,8-octanediamine) and 13.92 kg of diphenyl carbonate, 3.22 kg of phenol was mixed with isophorone diamine and fed into the reactor. Otherwise, the corresponding carbamate was synthesized from isophorone diamine using the same method as in the procedure (1-1) of Synthesis Example 1-1. The reaction solution was heated to 120°C and the internal pressure was set to 1.0 kPa, thereby removing 9.4 kg of phenol from the liquid.

[0879] The solution following the reaction (hereinafter referred to as "reaction solution (13-1)") was analyzed by liquid chromatography, and the carbamate compound corresponding to isophorone diamine was generated in 99% by mass. The mass of the above reaction solution (13-1) was 14.29 kg.

[0880] 2. Process (13-2): Thermal decomposition process of carbamate compounds

[0881] Using 14.29 kg of reaction solution (13-2) and 14.29 kg of diphenyl carbonate, reaction solution (13-2) was fed into the reactor over approximately 11 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.9, and pressure 20 to 29 kPa. After all of reaction solution (13-2) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution after the reaction was 23.44 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (13-2)") was purified using a column fractionation apparatus to separate the carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-22a) to (I-22b) (hereinafter, this mixture is sometimes referred to as "mixture (I-22)").

[0882] [Chemistry 90]

[0883]

[0884] In addition, analysis by NMR and gas chromatography showed that isophorone diisocyanate (IPDI) was generated in a yield of 75% by mass.

[0885] 3. Process (13-3): Light-boil separation process

[0886] The reaction solution (13-2) was continuously fed at a rate of 4.69 kg / h, and the discharge rate from line 34 under steady-state conditions was 0.80 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.98 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that IPDI was recovered in 82% by mass relative to the supplied reaction solution (13-2).

[0887] 4. Process (13-4): High-boiling-point separation process

[0888] Using the liquid recovered from storage tank 303 in step (13-3), the operating temperature was set to 190°C and the internal pressure to 0.3 kPa. High-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.18 kg of liquid was recovered into storage tank 402, with an IPDI recovery rate of 120% by mass.

[0889] [Synthesis Example 1-14]

[0890] (Preparation of XDI and its corresponding carbonyl compound (I-23))

[0891] 1. Process (14-1): Manufacturing process of carbamate compounds

[0892] Using 3.33 kg of phenylenediamine (instead of 4-aminomethyl-1,8-octanediamine) and 17.42 kg of diphenyl carbonate, 4.45 kg of phenol was mixed with phenylenediamine and fed into the reactor. Otherwise, the corresponding carbamate was synthesized from phenylenediamine using the same method as in the procedure (1-1) of Synthesis Example 1-1. The reaction solution was heated to 120°C and the internal pressure was set to 1.0 kPa, thereby discharging 12.64 kg of phenol from the liquid.

[0893] The solution following the reaction (hereinafter referred to as "reaction solution (14-1)") was analyzed by liquid chromatography, and the carbamate compound corresponding to diphenylene dimethylamine was generated in 98% by mass. The mass of the above reaction solution (14-1) was 16.99 kg.

[0894] 2. Process (14-2): Thermal decomposition process of carbamate compounds

[0895] Using 16.99 kg of reaction solution (14-1) and 16.99 kg of diphenyl carbonate, reaction solution (14-1) was fed into the reactor over approximately 11 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.5, and pressure 20 to 29 kPa. After all of reaction solution (14-2) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution after the reaction was 28.89 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (14-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-23).

[0896] [Chemistry 91]

[0897]

[0898] In addition, analysis by NMR and gas chromatography showed that phenyl dimethyl diisocyanate (XDI) was generated in a yield of 78% by mass.

[0899] 3. Process (14-3): Light-boil separation process

[0900] The reaction solution (14-2) was continuously fed at a rate of 5.78 kg / h, and the discharge rate from line 34 under steady-state conditions was 0.87 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.98 kg of liquid was recovered into storage tank 303 and analyzed by NMR, LC, and gas chromatography. The results showed that XDI was recovered in 88% by mass relative to the supplied reaction solution (14-2).

[0901] 4. Process (14-4): High-boiling-point separation process

[0902] Using the liquid recovered from storage tank 303 in step (14-3), the operating temperature was set to 170°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.87 kg of liquid was recovered into storage tank 402, resulting in a XDI recovery rate of 125% by mass.

[0903] [Synthesis Example 1-15]

[0904] (Preparation of MDI and its corresponding carbonyl compound (I-13))

[0905] 1. Process (15-1): Manufacturing process of carbamate compounds

[0906] With pipeline 14 closed, 3.33 kg (16.8 mol) of 4,4'-diaminodiphenylmethane is supplied from storage tank 101 via pipeline 11 to the SUS-made reaction vessel 104 equipped with a flow guide plate, and 2.53 kg (27.0 mol) of phenol is supplied from storage tank 102 via pipeline 12 to the reaction vessel 104, and the mixture is stirred to homogenize it. Next, with pipeline 16 closed, 2.53 kg (27.0 mol) of phenol is supplied from storage tank 102 via pipeline 15 to the SUS-made reaction vessel 105 equipped with a flow guide plate, and 11.96 kg (55.6 mol) of diphenyl carbonate is supplied from storage tank 103 via pipeline 13 to the reaction vessel 105. The liquid temperature in reaction vessel 105 is adjusted to 65°C. After stirring to make it homogeneous, a mixture of 4,4'-diaminodiphenylmethane and phenol is supplied from reaction vessel 104 through pipeline 14 at an internal temperature not exceeding 70°C. After continuous stirring for 2 hours, the reaction liquid is heated to 120°C, making the internal pressure approximately 1 kPa. 7.58 kg of phenol in the liquid is then discharged into storage tank 107 through pipeline 17 and condenser A11.

[0907] The resulting solution (hereinafter referred to as "reaction solution (15-1)") was analyzed by liquid chromatography, and a carbamate compound corresponding to 4,4'-diaminodiphenylmethane was produced in 95% by mass. The reaction solution (15-1) was then transferred through line 16 to storage tank 106. The mass of reaction solution (15-1) was 12.77 kg.

[0908] 2. Process (15-2): Thermal decomposition process of carbamate compounds

[0909] Using 12.77 kg of reaction solution (15-1) and 12.77 kg of diphenyl carbonate, reaction solution (15-1) was fed into the reactor over approximately 10 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio, and pressure of 11 to 16 kPa. After all of reaction solution (15-1) was transferred, the phenol was discharged for an additional 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution transferred to storage tank 205 was 11.75 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (15-2)") was purified using a column fractionation apparatus to separate the carbonyl compound. The separated carbonyl compound is the compound represented by the following formula (I-13).

[0910] [Chemistry 92]

[0911]

[0912] In addition, analysis by NMR and gas chromatography showed that MDI was produced in a yield of 70% by mass.

[0913] 3. Process (15-3): Light-boiling separation process

[0914] The reaction solution (15-2) was continuously fed at a rate of 2.35 kg / h, and the discharge rate from line 34 under steady-state conditions was 1.97 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 9.87 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that MDI was recovered in 79% by mass relative to the supplied reaction solution (15-2).

[0915] 4. Process (15-4): High-boiling-point separation process

[0916] Using the liquid recovered from storage tank 303 in step (15-3), the operating temperature was set to 170°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.54 kg of liquid was recovered into storage tank 402, resulting in a MDI recovery rate of 130% by mass.

[0917] [Synthesis Example 1-16]

[0918] (The manufacture of TDI and its corresponding carbonyl compounds (I-24a) to (I-24b))

[0919] 1. Process (16-1): Manufacturing process of carbamate compounds

[0920] Using 3.33 kg of toluene-2,4-diamine (instead of 4-aminomethyl-1,8-octanediamine) and 19.41 kg of diphenyl carbonate, 5.15 kg of phenol was mixed with phenylenediamine and fed into the reactor. Otherwise, the corresponding carbamate was synthesized from toluene-2,4-diamine using the same method as in the procedure (1-1) of Synthesis Example 1-1. The reaction solution was heated to 120°C and the internal pressure was set to 1.0 kPa, thereby removing 14.49 kg of phenol from the liquid.

[0921] The solution following the reaction (hereinafter referred to as "reaction solution (16-1)") was analyzed by liquid chromatography, and the corresponding carbamate compound was generated in 96% by mass. The mass of the above reaction solution (16-1) was 18.54 kg.

[0922] 2. Process (16-2): Thermal decomposition process of carbamate compounds

[0923] Using 18.54 kg of reaction solution (16-1) and 18.54 kg of diphenyl carbonate, reaction solution (16-1) was fed into the reactor over approximately 11 minutes to initiate the reaction. The reaction was carried out within a range of 238°C jacket temperature, 230°C internal temperature, reflux ratio 4.7, and pressure 20 to 29 kPa. After all of reaction solution (16-1) was transferred, the phenol was discharged for another 3 hours. Otherwise, the thermal decomposition reaction was carried out using the same procedures as in Synthesis Example 1-1. The mass of the reaction solution after the reaction was 11.75 kg. A portion of this reaction solution (hereinafter referred to as "reaction solution (16-2)") was purified using a column fractionation apparatus to separate the carbonyl compounds. The separated carbonyl compounds were a mixture of compounds represented by the following formulas (I-24a) to (I-24b) (hereinafter, this mixture is sometimes referred to as "mixture (I-24)").

[0924] [Chemistry 93]

[0925]

[0926] In addition, analysis by NMR and gas chromatography showed that toluene diisocyanate (TDI) was produced in a yield of 71% by mass.

[0927] 3. Process (16-3): Light-boiling separation process

[0928] The reaction solution (16-2) was continuously fed at a rate of 2.35 kg / h, and the discharge rate from line 34 under steady-state conditions was 0.94 kg / h. Otherwise, light boiling separation was performed using the same procedure as in Synthesis Example 1-1. 4.70 kg of liquid was recovered into storage tank 303. Analysis by NMR, LC, and gas chromatography revealed that TDI was recovered in 85% by mass relative to the supplied reaction solution (16-2).

[0929] 4. Process (16-4): High-boiling-point separation process

[0930] Using the liquid recovered from storage tank 303 in step (16-3), the operating temperature was set to 160°C and the internal pressure to 0.3 kPa. Otherwise, high-boiling separation was performed using the same procedure as in Synthesis Example 1-1. 3.27 kg of liquid was recovered from storage tank 402, resulting in a TDI recovery rate of 119% by mass.

[0931] <Preparation of Carbamate Compound (III)>

[0932] [Synthesis example 2-1]

[0933] (Preparation of carbamate compounds (III-1a) to (III-24b))

[0934] To 100.0 g of each isocyanate compound, hydroxyl compound (V) of the type and mixing amount listed in the table below was added, and the mixture was reacted at 120 °C for 3 hours to synthesize carbamate compound (III) corresponding to each isocyanate compound.

[0935] It should be noted that carbamate compounds (III-1a) to (III-1c) are obtained in the form of a mixture (III-1), carbamate compounds (III-2a) to (III-2c) are obtained in the form of a mixture (III-2), carbamate compounds (III-3a) to (III-3c) are obtained in the form of a mixture (III-3), carbamate compounds (III-4a) to (III-4c) are obtained in the form of a mixture (III-4), carbamate compounds (III-5a) to (III-5b) are obtained in the form of a mixture (III-5), and ammonia... Carbamate compounds (III-7a) to (III-7b) are obtained in the form of a mixture of (III-7), carbamate compounds (III-8a) to (III-8b) are obtained in the form of a mixture of (III-8), carbamate compounds (III-10a) to (III-10b) are obtained in the form of a mixture of (III-10), carbamate compounds (III-22a) to (III-22b) are obtained in the form of a mixture of (III-11), and carbamate compounds (III-24a) to (III-24b) are obtained in the form of a mixture of (III-24). The structures of these carbamate compounds are described below.

[0936] [Table 1]

[0937]

[0938] [Examples 1-62 and Comparative Examples 1-6]

[0939] (Preparation of isocyanate compositions A-a1 to A-a46 and A-b1 to A-b6)

[0940] The types and contents of isocyanate compound (II), carbonyl compound (I), carbamate compound (III) and carbonate (IV) are mixed as shown in the following tables to obtain various isocyanate compositions.

[0941] It should be noted that the details of the types of isocyanate compound (II), carbonyl compound (I), carbamate compound (III), and carbonate compound (IV) used are as follows.

[0942] (Isocyanate compound (II))

[0943] As isocyanate compound (II), the following compound obtained by the above-described synthetic method is used.

[0944] TTI: 4-Isocyanate-methyl-1,8-octamethylene diisocyanate

[0945] LTI: 2-Isocyanate ethyl-2,6-diisocyanate hexanoate (lysine triisocyanate)

[0946] LDI: Lysine methyl ester diisocyanate

[0947] LDI-Et: Lysine Ethyl Ester Diisocyanate

[0948] HDI: Hexane diisocyanate

[0949] HMDI: Methylene bis(cyclohexyl isocyanate)

[0950] HXDI: 1,3-bis(isocyanate methyl)cyclohexane

[0951] PDI: Pentane diisocyanate

[0952] IPDI: 3-Isocyanate-methyl-3,5,5-trimethylcyclohexyl isocyanate

[0953] XDI: Diisocyanate xylene

[0954] MDI: Diphenylmethane diisocyanate

[0955] TDI: Toluene diisocyanate

[0956] (Carbonyl compound (I))

[0957] As carbonyl compound (I), compounds represented by formulas (I-1a) to (I-24b) obtained by the above-described synthetic method are used. It should be noted that the carbonyl compounds (I-1a) to (I-1c) are a mixture thereof (I-1), the carbonyl compounds (I-2a) to (I-2c) are a mixture thereof (I-2), the carbonyl compounds (I-3a) to (I-3c) are a mixture thereof (I-3), the carbonyl compounds (I-4a) to (I-4c) are a mixture thereof (I-4), and the carbonyl compounds (I-5a) to (I-5b) are a mixture thereof (I-5). The carbonyl compounds (I-7a) to (I-7b) are used in mixture (I-7), the carbonyl compounds (I-8a) to (I-8b) are used in mixture (I-8), the carbonyl compounds (I-10a) to (I-10b) are used in mixture (I-10), the carbonyl compounds (I-22a) to (I-22b) are used in mixture (I-11), and the carbonyl compounds (I-24a) to (I-24b) are used in mixture (I-24).

[0958] [Chemistry 94]

[0959]

[0960] [Chem. 95]

[0961]

[0962] [Chemistry 96]

[0963]

[0964] [Chemistry 97]

[0965]

[0966] [Chem. 98]

[0967]

[0968] [Chemistry 99]

[0969]

[0970] (Carbamate compound (III))

[0971] As the carbamate compound (III), the compounds represented by the following formulas (III-1a) to (III-24b) obtained by the above-described synthetic method are used. It should be noted that the carbamate compounds (III-1a) to (III-1c) are mixtures thereof (III-1), the carbamate compounds (III-2a) to (III-2c) are mixtures thereof (III-2), the carbamate compounds (III-3a) to (III-3c) are mixtures thereof (III-3), the carbamate compounds (III-4a) to (III-4c) are mixtures thereof (III-4), and the carbamate compounds (III-5a) to (III-5b) are mixtures thereof (III-5). The carbamate compounds (III-7a) to (III-7b) are used in mixtures thereof (III-7), the carbamate compounds (III-8a) to (III-8b) are used in mixtures thereof (III-8), the carbamate compounds (III-10a) to (III-10b) are used in mixtures thereof (III-10), the carbamate compounds (III-22a) to (III-22b) are used in mixtures thereof (III-11), and the carbamate compounds (III-24a) to (III-24b) are used in mixtures thereof (III-24).

[0972] [Chemistry 100]

[0973]

[0974] [Chemistry 101]

[0975]

[0976] [Chemistry 102]

[0977]

[0978] [Chemistry 103]

[0979]

[0980] [Chemistry 104]

[0981]

[0982] [Chemistry 105]

[0983]

[0984] (carbonate(IV))

[0985] As carbonate (IV), the following compounds are used.

[0986] DPC: Diphenyl carbonate

[0987] GAC: bis(2-methoxyphenyl) carbonate

[0988] DPCP: Bis(4-cumylphenyl) carbonate

[0989] The above-described preservation tests were performed on each of the obtained isocyanate compositions, and each was evaluated. The results are shown in the following tables.

[0990]

[0991]

[0992]

[0993]

[0994]

[0995] According to the tables above, in isocyanate compositions A-a1 to A-a62 (Examples 1 to 62) containing specific amounts of isocyanate compound (II) and carbonyl compound (I), coloring is sufficiently suppressed and storage stability is excellent.

[0996] Furthermore, in isocyanate compositions A-a1 to A-a8, A-a11 to A-a18 and A-a21 to A-a62 (Examples 1 to 8, 11 to 18 and 21 to 62) which further contain urethane compound (III) and carbonate compound (IV) in addition to isocyanate compound (II) and carbonyl compound (I), the color difference before and after storage is further reduced, the amount of modification is further reduced, and the storage stability is particularly excellent.

[0997] On the other hand, in isocyanate compositions A-b1 and A-b4 (Comparative Examples 1 and 4) where the content of isocyanate compound (II) relative to the total mass of the isocyanate composition is less than 97% by mass, the color difference before and after storage increases, the amount of modification also increases, and the storage stability is poor.

[0998] Additionally, the composition does not contain carbonyl compound (I), or the content of carbonyl compound (I) relative to the total mass of the isocyanate composition is greater than 1.0 × 10⁻⁶. 4 In the isocyanate compositions A-b2, A-b3, A-b5 and A-b6 (Comparative Examples 2, 3, 5 and 6) with mass ppm, the color difference before and after storage increased, the amount of modification also increased, and the storage stability was poor.

[0999] Industrial applicability

[1000] The carbonyl compound and its manufacturing method according to this embodiment provide novel carbonyl compounds. The method for manufacturing the isocyanate compound of this embodiment, using the aforementioned carbonyl compound, prevents the solidification of byproducts on the apparatus during the manufacturing of the isocyanate compound, thereby improving the yield of the isocyanate compound.

[1001] Furthermore, the isocyanate composition according to this embodiment can provide an isocyanate composition in which coloring is sufficiently suppressed and storage stability is excellent.

[1002] Explanation of symbols

[1003] 11,12,13,14,15,16,17,21,22,23,24,25,26,27,28,31,32,33,34,35,36,41,42,43: Pipelines

[1004] A11, A21, A31, A41: Condenser

[1005] A32: Reboiler

[1006] 101, 102, 103, 106, 107, 202, 204, 205, 302, 303, 402, 403: Storage tanks

[1007] 104, 105, 201: SUS reaction vessels with baffles

[1008] 203, 301: Multistage distillation column

[1009] 401: Thin-film distillation apparatus

Claims

1. Carbonyl compounds represented by the following general formula (I), [Chemistry 1] In general formula (I), R 11 The group represented by any of the following formulas (Ia-1) to (Ia-24): In each pattern, the wavy line represents a connecting key; R 12 It is phenyl, cumylphenyl, methoxyphenyl, or ethoxyphenyl; n11 is an integer greater than 1 and less than 4, n12 is an integer greater than 0 and less than 3 but not 0, and the sum of n11 and n12 is an integer greater than 2 and less than 5. The carbonyl compound is any one of the compounds represented by the following formulas: (I-1a) to (I-1c), (I-2a) to (I-2c), (I-3a) to (I-3c), (I-4a) to (I-4c), (I-5a) to (I-5c), (I-7a) to (I-7b), (I-8a) to (I-8b), (I-10a) to (I-10b), (I-13), (I-16), (I-19), (I-20), (I-21), (I-22a) to (I-22b), (I-23), and (I-24a) to (I-24b). 。 2. A method for manufacturing a carbonyl compound, which is the method for manufacturing a carbonyl compound according to claim 1, wherein, The method includes the following steps: The carbonyl compound is synthesized by mixing one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds with one or more compounds selected from the group consisting of carbonate compounds and hydroxyl compounds and heating the mixture.

3. The manufacturing method as described in claim 2, wherein, The isocyanate compound is a compound represented by the following general formula (II). [Chemistry 2] In general formula (II), R 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 n21 is an integer greater than 2 and less than 5, satisfying the relation: n21 = n11 + n12.

4. The manufacturing method as described in claim 2 or 3, wherein, The carbamate compound is a compound represented by the following general formula (III). [Chemistry 3] In general formula (III), R 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 ;R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 n31 is an integer greater than 1 and less than 8, n32 is an integer greater than 0 and less than 7, and the sum of n31 and n32 is an integer greater than 2 and less than 8, satisfying the relation: n31 + n32 = n11 + n12.

5. The manufacturing method as described in claim 2 or 3, wherein, The carbonate is a compound represented by the following general formula (IV). [Chemistry 4] In general formula (IV), R 41 and R 42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 .

6. The manufacturing method as described in claim 2 or 3, wherein, The hydroxyl compound is a compound represented by the following general formula (V). [Chemistry 5] In general formula (V), R 51 For a monovalent organic group, the following relationship is satisfied: R 51 =R 12 .

7. A method for manufacturing an isocyanate compound, comprising the following steps: In the presence of the carbonyl compound of claim 1, the reaction solution containing the isocyanate compound represented by the following general formula (II) is purified by distillation to continuously recover the isocyanate compound as a gaseous component. [Chemistry 6] In general formula (II), R 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 n21 is an integer greater than 2 and less than 5, satisfying the relation: n21 = n11 + n12.

8. An isocyanate composition, wherein, Relative to the total mass of the isocyanate composition, it contains: Isocyanate compounds of 97% or more by mass; and 2.0 ppm or more, 1.0 × 10 4 The carbonyl compound of claim 1 with a mass of less than ppm; and They are respectively 2.0 ppm or more and 1.0 × 10 4 The compounds selected from the group consisting of carbamate compounds and carbonates, with a mass concentration of less than ppm, are one or more compounds. The isocyanate compound and the carbonyl compound are different compounds. The carbamate compound is a compound represented by the following general formula (III). [Chemistry 9] In general formula (III), R 31 Organic groups with a valence of (n31+n32) satisfy the following relationship: R 31 =R 11 ;R 32 For a monovalent organic group, the following relationship is satisfied: R 32 =R 12 n31 is an integer greater than 1 and less than 8, n32 is an integer greater than 0 and less than 7, and the sum of n31 and n32 is an integer greater than 2 and less than 8, satisfying the relation: n31 + n32 = n11 + n12. The carbonate is a compound represented by the following general formula (IV). [Chemistry 10] In general formula (IV), R 41 and R 42 Each of the organic groups is independently monovalent and satisfies the following relationship: R 41 =R 42 =R 12 .

9. The isocyanate composition of claim 8, wherein, The isocyanate compound is a compound represented by the following general formula (II). [Chemistry 8] In general formula (II), R 21 For organic groups with an n21 valence, the following relationship is satisfied: R 21 =R 11 n21 is an integer greater than 2 and less than 5, satisfying the relation: n21 = n11 + n12.

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