WO2023080258A1 - カルボニル化合物、カルボニル化合物の製造方法、イソシアネート化合物の製造方法、及びイソシアネート組成物 - Google Patents

カルボニル化合物、カルボニル化合物の製造方法、イソシアネート化合物の製造方法、及びイソシアネート組成物 Download PDF

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WO2023080258A1
WO2023080258A1 PCT/JP2022/041614 JP2022041614W WO2023080258A1 WO 2023080258 A1 WO2023080258 A1 WO 2023080258A1 JP 2022041614 W JP2022041614 W JP 2022041614W WO 2023080258 A1 WO2023080258 A1 WO 2023080258A1
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group
isomer
less
compound
reaction
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French (fr)
Japanese (ja)
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弘一 中岡
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Asahi Kasei Corp
Asahi Chemical Industry Co Ltd
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Priority to EP22890078.3A priority Critical patent/EP4431491A4/en
Priority to JP2023558106A priority patent/JP7680560B2/ja
Priority to CN202280073805.1A priority patent/CN118302407A/zh
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
    • C07C271/66—Y being a hetero atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C263/00—Preparation of derivatives of isocyanic acid
    • C07C263/18—Separation; Purification; Stabilisation; Use of additives
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C265/00—Derivatives of isocyanic acid
    • C07C265/14—Derivatives of isocyanic acid containing at least two isocyanate groups bound to the same carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the present invention relates to a carbonyl compound, a method for producing a carbonyl compound, a method for producing an isocyanate compound, and an isocyanate composition.
  • Isocyanates are widely used as raw materials for manufacturing polyurethane foams, paints, adhesives, etc.
  • the main industrial production method of isocyanate is the reaction of an amine compound with phosgene (phosgene method), and almost all of the production in the world is produced by the phosgene method.
  • phosgene method has many problems.
  • R is an a-valent organic group
  • R' is a monovalent organic group
  • a is an integer of 1 or more.
  • R a to R h are each independently a monovalent organic group.
  • Polyurethanes having urethane bonds are mainly produced by the reaction of di- or more functional isocyanates and di- or more functional alcohols, and are polymers with excellent tensile strength, abrasion resistance, and oil resistance. , adhesives, paints, binders, etc. Among them, polyurethanes made from linear or cyclic aliphatic isocyanates are excellent in weather resistance and light resistance, and are used in fields requiring high appearance quality such as baking paints, automobile clear coating materials, and coil coating materials.
  • Diisocyanate which is a bifunctional isocyanate, may be used as the isocyanate.
  • diisocyanate is polymerized by the represented reaction and used as an isocyanate polymer.
  • R represents a divalent organic group and R' represents a trivalent organic group.
  • polyurethane when used in fields where appearance quality is required, polyurethane is required to have little coloration. For this purpose, it is important not only that there is no coloration in the polyurethane formation reaction, but also that the raw material isocyanate (bifunctional or higher functional isocyanate) is less colored.
  • isocyanate tends to be oxidized by oxygen in the air or the like, and tends to be deteriorated or colored.
  • the isocyanate tends to be colored due to the catalyst or solvent used in the polymerization reaction.
  • a method of suppressing the coloring of isocyanate there is a method of manufacturing and storing by sealing with nitrogen gas and shutting it off from the air, and a method of adding ultraviolet absorbers, antioxidants, etc. and storing it.
  • US Pat. No. 6,200,000 discloses a method of modifying isocyanates followed by treatment with peroxides in order to produce polyisocyanates for light-colored polyurethane lacquers.
  • Patent Document 14 a method of producing an isocyanate with reduced coloring by contacting a colored isocyanate with an ozone-containing gas is studied.
  • Patent Document 15 a method for producing an isocyanate with reduced coloring by irradiating a colored isocyanate with light having a wavelength of 200 to 600 nm is also studied.
  • the present invention has been made in view of the above circumstances, and provides a novel carbonyl compound, a method for producing the same, and a method for producing an isocyanate compound using the carbonyl compound.
  • Patent Documents 4 to 6 do not necessarily sufficiently reduce coloring, and isocyanates with further reduced coloring are desired.
  • distillation purification is a common method for purifying compounds, but isocyanate is heated during distillation purification, which may lead to coloration of the isocyanate or denaturation of the isocyanate.
  • the present invention has been made in view of the above circumstances, and provides an isocyanate composition that is sufficiently suppressed in coloration and has excellent storage stability.
  • R 11 is a (n11+n12)-valent organic group
  • R 12 is a monovalent organic group.
  • n11 is an integer of 1 or more and 8 or less
  • n12 is 0 or more and 7 or less.
  • the sum of n11 and n12 is an integer of 2 or more and 8 or less.
  • R 11 may have 1 or more and 4 or less ester groups or nitrogen atoms, or a divalent or more and tetravalent or less aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, or 6 carbon atoms; is a divalent or more and trivalent or less aromatic hydrocarbon group of 20 or less, and
  • R 11 may have 1 or more and 2 or less ester groups, or a bivalent or more and tetravalent or less aliphatic hydrocarbon group having 5 or more and 15 or less carbon atoms, or 6 or more and 15 or less carbon atoms; is an aromatic hydrocarbon group having a valence of 2 or more and 3 or less, R 12 is a monovalent aromatic hydrocarbon group having 6 or more and 15 or less carbon atoms, which may contain an oxygen atom;
  • the n 11 is an integer of 1 or more and 4 or less,
  • the n 12 is an integer of 0 or more and 3 or less, and
  • n31 is an integer of 1 or more and 8 or less
  • n32 is an integer of 0 or more and 7 or less
  • the sum of n31 and n32 is an integer of 2 or more and 8 or less
  • n31+n32 n11+n12.
  • reaction liquid containing the isocyanate compound represented by the following general formula (II) is purified by distillation, and the gas phase is continuously purified.
  • a method for producing an isocyanate compound comprising recovering said isocyanate compound as a component.
  • R 11 is a (n11+n12)-valent organic group
  • R 12 is a monovalent organic group.
  • n11 is an integer of 1 or more and 8 or less
  • n12 is 0 or more and 7 or less.
  • the sum of n11 and n12 is an integer of 2 or more and 8 or less.
  • R 11 may have 1 or more and 4 or less ester groups or nitrogen atoms, or a divalent or more and tetravalent or less aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms, or 6 carbon atoms; is a divalent or more and trivalent or less aromatic hydrocarbon group of 20 or less, and
  • the isocyanate composition according to (1) or (2), wherein the isocyanate compound is a compound represented by the following general formula (II).
  • n31 is an integer of 1 or more and 8 or less
  • n32 is an integer of 0 or more and 7 or less
  • the sum of n31 and n32 is an integer of 2 or more and 8 or less
  • n31+n32 n11+n12.
  • a novel carbonyl compound can be provided according to the carbonyl compound and the method for producing the same according to the above aspect.
  • the method for producing an isocyanate compound according to the aspect described above is a method using the carbonyl compound, and can prevent by-products from sticking to equipment during the production of the isocyanate compound, thereby improving the yield of the isocyanate compound.
  • the isocyanate composition of the above aspect it is possible to provide an isocyanate composition in which coloration is sufficiently suppressed and which has excellent storage stability.
  • FIG. 1 is a schematic configuration diagram showing an apparatus for producing a carbamate compound used in Examples.
  • FIG. 1 is a schematic configuration diagram showing a pyrolysis reactor used in Examples.
  • FIG. 1 is a schematic configuration diagram showing a low boiling point separation apparatus used in Examples.
  • FIG. 1 is a schematic configuration diagram showing a high-boiling separator used in Examples.
  • FIG. 1 is a graph showing NMR spectra of carbamate compounds (I-1a) to (I-1c) produced in Example 1-1.
  • 1 is a graph showing NMR spectra of carbamate compounds (I-3a) to (I-3c) produced in Example 1-7.
  • 1 is a graph showing the results of gas chromatography-mass spectrometry of carbamate compounds (I-3a) to (I-3c) produced in Example 1-7.
  • organometallic compounds also include organometallic compounds and metal complexes.
  • terms such as "organic group” and “substituent” mean groups composed of atoms that do not contain metal atoms and/or semimetals. Further, in the present embodiment, preferably H (hydrogen atom), C (carbon atom), N (nitrogen atom), O (oxygen atom), S (sulfur atom), Cl (chlorine atom), Br (bromine atom) , I (iodine atom).
  • aliphatic and “aromatic” are used frequently. According to the IUPAC rules mentioned above, it is stated that organic compounds are classified into aliphatic compounds and aromatic compounds. Aliphatic is the definition of the group according to the 1995 IUPAC Recommendations for aliphatic compounds. The recommendation defines aliphatic compounds as "Acyclic or cyclic, saturated or unsaturated carbon compounds, excluding aromatic compounds".
  • the "aliphatic compound” used in the description of the present embodiment contains both saturated and unsaturated, chain and cyclic, and the above 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).
  • H hydrogen atom
  • C carbon atom
  • N nitrogen atom
  • O oxygen atom
  • S sulfur atom
  • Si silicon atom
  • Cl chlorine atom
  • Br bromine atom
  • I iodine atom
  • an aromatic group such as an aralkyl group
  • the term "aliphatic group substituted with an aromatic group” or "group consisting of an aliphatic group to which an aromatic group is bonded” is used. may be indicated. This is based on the reactivity in the present embodiment, and is because the reactive properties of groups such as aralkyl groups are very similar to the reactivity of aliphatic rather than aromatic groups.
  • non-aromatic reactive groups including aralkyl groups, alkyl groups, etc. are defined as "aliphatic groups optionally substituted with aromatic groups” and "aliphatic groups optionally bonded with aromatic groups”. etc.
  • active hydrogen refers to hydrogen atoms (excluding aromatic hydroxy groups) bonded to oxygen atoms, sulfur atoms, nitrogen atoms, silicon atoms, etc., and hydrogen atoms of terminal methine groups.
  • the compound having a hydroxy group includes alcohols and aromatic hydroxy compounds.
  • alcohol refers to "Compounds in which a hydroxy group, -OH, is attached to a saturated carbon atom: R3COH)” and does not include aromatic hydroxy compounds in which a hydroxy group is bonded to an aromatic ring.
  • aromatic hydroxy compound refers to phenols described in the IUPAC definition (Rule C-202) "one or more hydroxy groups attached to a benzene ring or other arene ring. "Compounds having one or more hydroxy groups attached to a benzene or other arene ring.”
  • the carbonyl compound of the present embodiment is a compound represented by the following general formula (I) (hereinafter sometimes referred to as "carbonyl compound (I)").
  • R 11 is a (n11+n12)-valent organic group
  • R 12 is a monovalent organic group.
  • n11 is an integer of 1 or more and 8 or less
  • n12 is 0 or more and 7 or less.
  • the sum of n11 and n12 is an integer of 2 or more and 8 or less.
  • the inventors have found that the carbonyl compound (I) is produced in the production of isocyanate compounds by the thermal decomposition reaction of carbamate compounds.
  • the isocyanate compound is produced by thermal decomposition from the carbamate compound, the coexistence of the carbonyl compound (I) allows side-reactants having a boiling point higher than that of the isocyanate compound (The present inventors have found that it is possible to prevent adhesion of the high-boiling-point side-reactant), efficiently recover the isocyanate compound, and improve the yield of the isocyanate compound, thereby completing the present invention.
  • R 11 is a (n11+n12)-valent organic group, that is, an organic group having a valence of 2 or more and 8 or less.
  • R 11 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an ester group of 1 to 4 carbon atoms or a nitrogen atom, or 6 or more carbon atoms. It is preferably an aromatic hydrocarbon group having a valence of 20 or less and having a valence of 20 or more and 3 or less.
  • the aliphatic hydrocarbon group for R 11 includes an alkylene group or an alkanetriyl group, a cycloalkyl group, a cycloalkylene group or a cycloalkanetriyl group, or the alkyl group, the alkylene group or the alkanetriyl group, A group composed of the cycloalkyl group, the cycloalkylene group or the cycloalkanetriyl group is preferable, and a linear or branched alkylene group or alkanetriyl group, cycloalkylene group or cycloalkanetriyl group , or a group composed of the alkylene group or the alkanetriyl group and the cycloalkyl group, the cycloalkylene group or the cycloalkanetriyl group is more preferable.
  • linear or branched alkylene groups examples include methylene, ethylene, propylene, trimethylene, pentylene, n-hexylene and decamethylene groups.
  • the cycloalkylene group includes, for example, a cyclobutylene group, a cyclohexylene group, and the like.
  • linear or branched alkanetriyl groups examples include hexanetriyl, nonanetriyl, and decantriyl groups.
  • the cycloalkanetriyl group includes, for example, a cyclopropanetriyl group, a cyclobutanetriyl group, a cyclopentanetriyl group, a cyclohexanetriyl group, and the like.
  • the aromatic hydrocarbon group for R 11 is preferably a substituted or unsubstituted group having an aromatic ring having 6 or more and 13 or less carbon atoms.
  • substituents include alkyl groups, aryl groups, and aralkyl groups.
  • the aromatic ring may be an aromatic hydrocarbon ring or a heteroaromatic ring, and specific examples thereof include benzene ring, naphthalene ring, pyridine ring and the like.
  • R 11 is an amine compound having an ester group obtained by reacting the carboxy group of an amino acid with a hydroxy compound. is preferably a group other than the terminal primary amino group.
  • amine compound having an ester group examples include, for example, acrylic acid-2-aminoethyl ester, 2-methyl-acrylic acid-2-aminoethyl ester, acrylic acid-2-aminopropyl ester, 2- Methyl-Acrylic Acid-2-Aminopropyl Ester, Acrylic Acid-3-Aminopropyl Ester, 2-Methyl-Acrylic Acid-3-Aminopropyl Ester, Acrylic Acid-4-Aminobutyl Ester, 2-Methyl-Acrylic Acid-4 -aminobutyl ester, 5-aminopentyl acrylate, 2-methyl-5-aminopentyl acrylate, 6-aminohexyl acrylate, 2-methyl-6-aminohexyl acrylate, acrylic Acid-8-aminoctyl ester, 2-methyl-acrylic acid-8-aminoctyl ester, acrylic acid-10-aminodecyl ester, 2-methyl-acrylic
  • amino acids used for producing amine compounds having an ester group include lysine, alanine, arginine, asparagine, glutamine, glycine, aspartic acid, glutamic acid, ornithine, histidine, isoleucine, leucine, methionine, phenylalanine, tryptophan, and valine. mentioned.
  • the amino acid is preferably lysine, arginine, glycine, aspartic acid, glutamic acid or ornithine, more preferably lysine, arginine, glycine, aspartic acid or glutamic acid.
  • Hydroxy compounds used in the production of amine compounds having an ester group include alcohols and aromatic hydroxy compounds.
  • alcohols include methyl alcohol, ethanol, propyl alcohol, butyl alcohol, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, lauryl alcohol, dodecyl alcohol, stearyl alcohol, eicosyl alcohol, allyl alcohol, crotyl alcohol, propargyl alcohol, cyclopentanol, cyclohexanol, benzyl alcohol, cinnamyl alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, 1,3-butanediol, 1,4-butanediol, hydrogenated bisphenol A, neopentyl glycol, glycerin, trimethylolpropane, pentaerythritol
  • aromatic hydroxy compounds examples include phenol (carbolic acid), 2-methoxyphenol, cresol, xylenol, carvacrol, motyl, monophenols such as naphthol, catechol, resorcinol, hydroquinone, bisphenol A, bisphenol F, pyrogallol, phloroglucin. and polyhydric phenols such as
  • R 11 When the aliphatic hydrocarbon group or aromatic group for R 11 has 1 or more and 4 or less nitrogen atoms, R 11 includes a secondary or tertiary amine in addition to the terminal of the aliphatic hydrocarbon group or aromatic group. It is preferably an organic group obtained by removing the terminal amino group from an amine compound having 1 or more and 4 or less.
  • amine compound having 1 to 4 secondary or tertiary amines other than the end of the aliphatic hydrocarbon group or aromatic group herein include, for example, 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 , trisaminoethylamine, trisaminopropylamine, and the like.
  • the amine compound is preferably an amine compound having one or more and two or less tertiary amines in addition to the terminal and an aliphatic hydrocarbon group or an aromatic group, and a tertiary amine other than one terminal. and an aliphatic hydrocarbon group or an aromatic group.
  • R 11 is preferably a group represented by any one of the following formulas (Ia-1) to (Ia-24), such as formulas (Ia-1), (Ia-2), (Ia-3 ), (Ia-14), (Ia-18), or (Ia-19).
  • formulas (Ia-1) to (Ia-24) such as formulas (Ia-1), (Ia-2), (Ia-3 ), (Ia-14), (Ia-18), or (Ia-19).
  • a wavy line indicates a bond.
  • R 12 is a monovalent organic group, preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, which may contain an oxygen atom.
  • Aliphatic hydrocarbon groups for R 12 include, for example, methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), hexyl group (each isomer) , heptyl group (each isomer), octyl group (each isomer), nonyl group (each isomer), decyl group (each isomer), undecyl group (each isomer), dodecyl group (each isomer), tridecyl group (each isomer), tetradecyl group (each isomer), pentadecyl group (each isomer), hexadecyl group (each isomer), heptadecyl group (each isomer), octadecyl group (each isomer), nonadecyl (each isomer),
  • the aliphatic hydrocarbon group which may contain an oxygen atom for R 12 includes, for example, a methoxymethyl group, a methoxyethyl group (each isomer), a methoxypropyl group (each isomer), a methoxybutyl group (each isomer), Methoxypentyl group (each isomer), methoxyhexyl group (each isomer), methoxyheptyl group (each isomer), methoxyoctyl group (each isomer), methoxynonyl group (each isomer), methoxydecyl group (each isomer), methoxyundecyl group (each isomer), methododecyl group (each isomer), methoxytridecyl group (each isomer), methoxytetradecyl group (each isomer), methoxypentadecyl group (each isomer isomer
  • aromatic hydrocarbon group for R 12 examples include aryl groups such as phenyl group, naphthyl group, anthryl group, pyrenyl group and phenanthryl group; methylphenyl group (each isomer), ethylphenyl group (each isomer), Propylphenyl group (each isomer), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer) , tetradecylphen
  • Examples of the aromatic hydrocarbon group which may contain an oxygen atom for R 12 include alkoxyaryl groups such as a methoxyphenyl group (each isomer) and an ethoxyphenyl group (each isomer).
  • R 12 includes phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer), butyl Phenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer) isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer
  • n11 is an integer of 1 or more and 8 or less.
  • n12 represents the number of isocyanate groups and is an integer of 0 or more and 7 or less.
  • the sum of n11 and n12 (n11+n12) is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably an integer of 3 or more and 4 or less.
  • the value of (n11+n12) increases, the molecular weight of the carbonyl compound (I) increases, the boiling point also increases, and separation from the isocyanate becomes easier.
  • (n11+n12) is preferably 6 or less, more preferably 5 or less, and even more preferably 4 or less (n11+n12).
  • Preferred carbonyl compounds (I) include, for example, compounds represented by the following formulas (I-1a) to (I-24) (hereinafter sometimes referred to as "carbonyl compounds (I-1a)" and the like), and the like. mentioned. Incidentally, carbonyl compounds (I-1a) ⁇ (I-1c), carbonyl compounds (I-2a) ⁇ (I-2c), carbonyl compounds (I-3a) ⁇ (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), Carbonyl compounds (I-8a) ⁇ (I-8b), carbonyl compounds (I-9a) ⁇ (I-9b), carbonyl compounds (I-10a) ⁇ (I-10b), carbonyl compounds (I-11a) ⁇ (I-11b), carbonyl compounds (I-12a) to (I-12b), carbon
  • the method for producing a carbonyl compound of the present embodiment includes one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds, one or more compounds selected from the group consisting of carbonate esters and hydroxy compounds; and heating to synthesize said carbonyl compound.
  • the production method of the carbonyl compound of the present embodiment includes: 1) a production method by a thermal decomposition reaction of a carbamate compound; 2) one or more compounds selected from the group consisting of an isocyanate compound and a carbamate compound; One or more compounds selected from the group consisting of compounds are mixed and heated.
  • the production reaction of the carbonyl compound (I) involves the reaction of one or more compounds selected from the group consisting of isocyanate compounds and carbamate compounds and one or more compounds selected from the group consisting of carbonate esters and hydroxy compounds. Produced in a reaction. Therefore, in the thermal decomposition reaction of the carbamate compound, the amount of carbonate ester used is increased, or the thermal decomposition reaction is performed under reflux conditions to prevent excess evaporation of carbonate ester, thereby relatively producing carbonyl compound (I). You can increase the ratio.
  • the carbonyl compound (I) is presumed to be produced by the reaction mechanism represented by the following formula (F), (G) or (H).
  • R j is a divalent or higher valent organic group.
  • R k is a monovalent organic group.
  • the amount (molar amount) of the carbonate ester used as a solvent is preferably as large as possible from the viewpoint of suppressing side reactions. 0.001 times or more and 100 times or less is preferable, 0.01 times or more and 80 times or less is more preferable, and 0.1 times or more and 50 times or less is even more preferable.
  • the carbonate ester may be used as it is, or the carbonate ester may be newly added to the carbamate compound. Also, the carbonate ester may be fed to the reactor before the reaction starts, may be fed during the reaction, or both. Among them, it is preferable to supply to the reactor before the reaction.
  • the reaction temperature is usually 100° C. or higher and 400° C. or lower, and a high temperature is preferable in order to increase the reaction rate. Since the above-mentioned compounds may cause side reactions as described above, the temperature is preferably 130° C. or higher and 300° C. or lower, more preferably 150° C. or higher and 280° C. or lower. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually carried out in the range of 20 Pa or more and 1 ⁇ 10 6 Pa or less.
  • reaction time is not particularly limited, and is usually 0.001 hours or more and 100 hours or less, preferably 0.01 hours or more and 50 hours or less, and 0.1 hours or more and 10 hours or less. more preferred.
  • a catalyst can be used, and the amount of the catalyst used is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, relative to the mass of the carbamate compound.
  • catalysts include organometallic catalysts such as dibutyltin dilaurate, lead octylate and stannous octoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine and triethylamine.
  • organometallic catalysts such as dibutyltin dilaurate, lead octylate and stanaoctoate are preferred. These compounds may be used alone or as a mixture of two or more.
  • the thermal decomposition reaction is a reaction that produces the corresponding isocyanate compound, hydroxy compound, and carbonyl compound from the carbamate compound.
  • the hydroxy compound which is the product of the thermal decomposition reaction, is taken out as a gas phase component from the thermal decomposition reaction system by, for example, distillation, and refluxed. It is preferable to separate the hydroxy compound from the carbonate ester and the isocyanate compound under such conditions as to allow the carbonate ester and the isocyanate to exist as liquid phase components.
  • the low-boiling components may be distilled off, and the distillation method is not particularly limited as long as the low-boiling components can be separated as gas phase components.
  • the pressure for distilling off the low-boiling components varies depending on the type of compound and the reaction temperature. , 20 Pa or more and 1 ⁇ 10 6 Pa or less is preferable, 20 Pa or more and 1 ⁇ 10 4 Pa or less is more preferable, 20 Pa or more and 1 ⁇ 10 3 Pa or less is more preferable, and 20 Pa or more and 1 ⁇ 10 2 Pa or less is particularly preferable.
  • the operation time (residence time in the case of a continuous method) when distilling off the light boiling components is not particularly limited as long as the separation of the carbonyl compounds and the light boiling components is possible, and side reactions with the carbonyl compounds are suppressed. From the viewpoint, it is preferably 5 seconds or more and 100 hours or less, more preferably 10 seconds or more and 50 hours or less, and even more preferably 20 seconds or more and 10 hours or less.
  • the temperature at which the low-boiling components are distilled off is not particularly limited as long as the carbonyl compounds are stable and the carbonyl compounds can be separated from the low-boiling components. 300° C. or higher is preferable, 30° C. or higher and 280° C. or lower is more preferable, and 40° C. or higher and 250° C. or lower is even more preferable.
  • the carbonyl compound (I) is a mixture of the isocyanate compound (II) and the carbonate ester (IV) , a mixture of carbamate compound (III) or carbamate compound (VI) and carbonate ester (IV), a mixture of isocyanate compound (II), hydroxy compound (V) and carbonate ester (IV), isocyanate compound (II) and carbamate compound ( III) or a mixture of carbamate compound (VI) and carbonate ester (IV), or a mixture of isocyanate compound (II) and carbamate compound (III) or carbamate compound (VI), carbonate ester (IV) and hydroxy compound (V) (Hereinafter, these mixtures may be collectively simply referred to as “raw material mixture”).
  • the compounding amount (molar amount) of the carbonate ester is preferably as large as possible from the viewpoint of suppressing side reactions. It is preferably 100 times or less, more preferably 0.01 times or more and 80 times or less, and even more preferably 0.1 times or more and 50 times or less.
  • the heating temperature is usually 100° C. or higher and 400° C. or lower, and a high temperature is preferable in order to increase the reaction rate. Since the above-mentioned compounds may cause side reactions as described above, the temperature is preferably 130° C. or higher and 300° C. or lower, more preferably 150° C. or higher and 280° C. or lower. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.
  • the pressure during heating varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually carried out in the range of 20 Pa or more and 1 ⁇ 10 6 Pa or less.
  • the heating time is not particularly limited, and is usually 0.001 hours or more and 100 hours or less, preferably 0.01 hours or more and 50 hours or less, and 0.1 hours or more and 10 hours or less. more preferred.
  • the rate and amount of carbonyl compounds produced can be increased by heating the raw material mixture in contact with stainless steel.
  • stainless steel SUS316 or SUS304 can be used regardless of the shape, and for example, fillers and metal pieces are preferably used.
  • the packing is not particularly limited, but DIXON Packing, McMAHON Packing, Coil PACK, MESH RING, CANNON Packing, HELI PACK, RASCHIG RING, PRICKLE RING, etc. are used.
  • the volume of the raw material liquid of the carbonyl compound is V and the surface area of the stainless steel is A
  • the larger the contact area with the stainless steel per unit volume of the raw material liquid the faster the rate of generation of the carbonyl compound.
  • the value of A/V is preferably 0.001 m 2 /m 3 or more and 100000 m 2 /m 3 or less, more preferably 0.01 m 2 /m 3 or more and 50000 m 2 /m 3 or less, and 0.1 m 2 /m 3 or more and 10000 m 2 /m 3 or less is more preferable.
  • reaction format is not particularly limited, a reactor that can efficiently mix and heat the raw material mixture or the mixture and stainless steel is preferable.
  • a method of heating the raw material mixture in a stainless steel stirring tank or distillation tower is preferable.
  • the low-boiling components may be distilled off, and the distillation method is not particularly limited as long as the low-boiling components can be separated as gas phase components.
  • the term "low-boiling component (low-boiling point component)" as used herein refers to a component having a boiling point lower than that of the carbonyl compound, and varies depending on the type of compound used as the raw material for the production of the carbonyl compound, but is mainly the carbonate ester contained in the raw material mixture. , an isocyanate compound generated by a thermal decomposition reaction, and one or more compounds selected from the group consisting of a hydroxy compound.
  • the pressure for distilling off the low-boiling components varies depending on the type of compound and the reaction temperature. , 20 Pa or more and 1 ⁇ 10 6 Pa or less is preferable, 20 Pa or more and 1 ⁇ 10 4 Pa or less is more preferable, 20 Pa or more and 1 ⁇ 10 3 Pa or less is more preferable, and 20 Pa or more and 1 ⁇ 10 2 Pa or less is particularly preferable.
  • the operation time (residence time in the case of a continuous method) when distilling off the light boiling components is not particularly limited as long as the separation of the carbonyl compounds and the light boiling components is possible, and side reactions with the carbonyl compounds are suppressed. From the viewpoint, it is preferably 5 seconds or more and 100 hours or less, more preferably 10 seconds or more and 50 hours or less, and even more preferably 20 seconds or more and 10 hours or less.
  • the temperature at which the low-boiling components are distilled off is not particularly limited as long as the carbonyl compounds are stable and the carbonyl compounds can be separated from the low-boiling components. 300° C. or higher is preferable, 30° C. or higher and 280° C. or lower is more preferable, and 40° C. or higher and 250° C. or lower is even more preferable.
  • isocyanate compound (II) a compound represented by the following general formula (II) (hereinafter sometimes referred to as "isocyanate compound (II)”) is preferably used.
  • R 21 is an aliphatic hydrocarbon group
  • specific examples of the isocyanate compound (II) include aliphatic diisocyanates, aliphatic triisocyanates, and substituted cycloaliphatic polyisocyanates. .
  • aliphatic diisocyanates examples include diisocyanatoethane, diisocyanatopropane (each isomer), diisocyanatobutane (each isomer), diisocyanatopentane (each isomer), diisocyanatohexane (each isomer), diisocyanatodecane (each isomer), and the like.
  • aliphatic triisocyanates examples include triisocyanatohexane (each isomer), 4-isocyanatomethyl-1,8-octamethylene diisocyanate, triisocyanatononane (each isomer), triisocyanatodecane (each isomer) and the like.
  • Substituted cycloaliphatic polyisocyanates include, for example, diisocyanatocyclobutane (each isomer), diisocyanatocyclohexane (each isomer), 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate (also called isophorone diisocyanate) (each isomer), 1,3-bis(isocyanatomethyl)cyclohexane (at least one of cis and trans isomers), methylenebis(cyclohexyl isocyanate) (also called dicyclohexylmethane diisocyanate) ) (each isomer) and the like.
  • diisocyanatocyclobutane each isomer
  • diisocyanatocyclohexane each isomer
  • 3-isocyanatomethyl-3,5,5-trimethylcyclohexylisocyanate also called isophorone diisocyanate
  • R 21 is an aromatic group
  • specific examples of the isocyanate compound (II) include aromatic diisocyanates and aromatic triisocyanates.
  • aromatic diisocyanates include diisocyanatobenzene (each isomer), diisocyanatotoluene (each isomer), bis(isocyanatophenyl)methane (each isomer), diisocyanatomesitylene (each isomer ), diisocyanatobiphenyl (each isomer), diisocyanatodibenzyl (each isomer), bis(isocyanatophenyl)propane (each isomer), bis(isocyanatophenyl)ether (each isomer), bis (isocyanatophenoxyethane) (each isomer), diisocyanatoxylene (each isomer), diisocyanatoanisole (each isomer), diisocyanatophenetol (each isomer), diisocyanatonaphthalene (each isomer) isomer), diisocyanatomethylbenzene (each is
  • aromatic triisocyanates examples include triisocyanatobenzene (each isomer), triisocyanato-methylbenzene (each isomer), tris(isocyanatopropan-yl)benzene (each isomer), tris(isocyanate Natopropan-yl)-methylbenzene (each isomer), Tris(isocyanatomethyl)-methylbenzene (each isomer), ((isocyanato-phenylene)bis(methylene))bis(isocyanatobenzene) (each isomer) etc.
  • the electron-withdrawing effect of the aromatic group increases the reactivity of the directly attached isocyanate group. Furthermore, as the number of isocyanate groups directly bonded to the same aromatic compound increases, the reactivity increases due to mutual electron attraction. From the viewpoint of reactivity, the number of isocyanate groups for R 21 is preferably 2 or more, more preferably 3 or more. On the other hand, when the reactivity of the isocyanate increases, the reaction between moisture, the isocyanate itself, and other impurities occurs, and the stability of the compound at room temperature and during heating decreases. From the viewpoint of the stability of the isocyanate compound, the number of isocyanate groups directly bonded to R 21 is preferably 4 or less, more preferably 3 or less.
  • the isocyanate compound (II) include acrylic acid-2-isocyanato-ethyl ester , 2-methyl-acrylic acid-2-isocyanato-ethyl ester, acrylic acid-2-isocyanato-propyl ester, 2-methyl-acrylic acid-2-isocyanato-propyl ester, acrylic acid-3-isocyanato-propyl ester, 2 -methyl-acrylic acid-3-isocyanato-propyl ester, acrylic acid-4-isocyanato-butyl ester, 2-methyl-acrylic acid-4-isocyanato-butyl ester, acrylic acid-5-isocyanato-pentyl ester, 2-methyl - acrylic acid 5-isocyanato-pentyl ester, acrylic acid 6-isocyanato-hexyl ester, 2-methyl-acrylic acid 6-isocyana
  • the reactivity of the isocyanate group is improved.
  • the carbon-carbon or carbon-nitrogen bond between the isocyanate group, which is an electron-withdrawing group, and the ester group or nitrogen atom is likely to dissociate, which may impair the thermal stability of the compound.
  • the number of carbon atoms is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more.
  • the isocyanate compound (II) is often used as a raw material for paints and is required to have a property (weather resistance) that it does not color when exposed to light such as sunlight.
  • R 21 has an aromatic group, coloration may occur due to absorption of light energy when exposed to sunlight.
  • R 21 preferably does not have an aromatic group, and may have an ester group of 1 or more and 4 or less or a nitrogen atom, and has 1 or more and 20 or less carbon atoms. More preferably, it is an aliphatic hydrocarbon group having a valence of 4 or more and 4 or less.
  • R 21 is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and the groups represented by the formulas (Ia-1), (Ia-2), ( A group represented by Ia-3), (Ia-14), (Ia-18), or (Ia-19) is more preferable.
  • n21 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably an integer of 3 or more and 4 or less.
  • a polymer can be obtained by reacting an isocyanate having a valence of n21 or higher with a dihydroxy compound or diamine compound having an active hydrogen group.
  • n21 As the value of n21 increases, the number of cross-linking points (isocyanate groups) per isocyanate molecule increases, so the cross-linking density when polymerized increases, shortening the curing time and improving the hardness of the polymer.
  • the crosslink density is increased means that the average molecular chain length between the crosslink points is decreased. If the number of isocyanate groups in the isocyanate molecule is 3 or more (n21 is 3 or more), the linear polymer can be further bonded to the polymer, and the molecular weight of the polymer tends to increase. can be expected to dramatically improve the physical properties of the polymer.
  • isocyanate production when a highly reactive isocyanate compound is heated, a modification reaction occurs, which causes sticking or clogging in equipment. is preferred, 5 or less is more preferred, and 4 or less is even more preferred.
  • Preferred isocyanate compounds (II) include, for example, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanatoethyl-2,6-diisocyanatohexanoate (LTI), lysine methyl ester diisocyanate (LDI), methylenebis(cyclohexylisocyanate) (HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), diisocyanatodiphenylmethane (MDI) and the like.
  • TTI 4-isocyanatomethyl-1,8-octamethylene diisocyanate
  • LKI 2-isocyanatoethyl-2,6-diisocyanatohexanoate
  • LKI lysine methyl ester diisocyanate
  • HMDI methylenebis(cyclohexylisocyanate)
  • HXDI 1,
  • carbamate compound (III) 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 referred to as “carbamate compound (VI)”) is preferably used.
  • n31 is an integer of 1 or more and 8 or less
  • n32 is an integer of 0 or more and 7 or less
  • the sum of n31 and n32 is an integer of 2 or more and 8 or less
  • n31+n32 n11+n12.
  • R 31 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have an ester group of 1 or more and 4 or less or a nitrogen atom, or 6 or more carbon atoms. It is preferably an aromatic hydrocarbon group having a valence of 20 or less and having a valence of 20 or more and 3 or less.
  • R 31 is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and the groups represented by the formulas (Ia-1), (Ia-2), ( A group represented by Ia-3), (Ia-14), (Ia-18), or (Ia-19) is more preferable.
  • R 32 is preferably an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms or an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms, which may contain an oxygen atom.
  • R 32 examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer ), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), methyl
  • n31 is an integer of 1 or more and 8 or less.
  • n32 is an integer of 0 or more and 7 or less.
  • Preferred carbamate compounds (III) include, for example, compounds represented by the following formulas (III-1a) to (III-24b).
  • Each can be
  • R 61 is an ester group having 1 to 4 carbon atoms or an aliphatic hydrocarbon group having 1 to 20 carbon atoms and having 1 to 20 carbon atoms and having 2 to 4 valences, or an aliphatic hydrocarbon group having 6 or more carbon atoms. It is preferably an aromatic hydrocarbon group having a valence of 20 or less and having a valence of 20 or more and 3 or less.
  • R 61 is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and the groups represented by the formulas (Ia-1), (Ia-2), ( A group represented by Ia-3), (Ia-14), (Ia-18), or (Ia-19) is more preferred.
  • R 62 is preferably an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms or an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms, which may contain an oxygen atom.
  • R 62 examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer ), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer),
  • n61 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably an integer of 3 or more and 4 or less.
  • Preferred carbamate compounds (VI) include, for example, compounds represented by the following formulas (VI-1) to (VI-24).
  • Carbonate ester a compound represented by the following general formula (IV) (hereinafter sometimes referred to as “carbonate ester (IV)”) is preferably used.
  • R 41 and R 42 are preferably substituted or unsubstituted aryl groups.
  • Preferred carbonate esters (IV) include, for example, diphenyl carbonate, bis(4-cumylphenyl) carbonate, bis(2-methoxyphenyl) carbonate, bis(2-ethoxyphenyl) carbonate and the like.
  • hydroxy compound (V) a compound represented by the following general formula (V) (hereinafter sometimes referred to as "hydroxy compound (V)”) is preferably used.
  • R 51 is preferably an aliphatic hydrocarbon group having 1 or more and 20 or less carbon atoms or an aromatic hydrocarbon group having 6 or more and 20 or less carbon atoms, which may contain an oxygen atom.
  • R 51 examples include phenyl group, naphthyl group, anthryl group, pyrenyl group, phenanthryl group, methylphenyl group (each isomer), ethylphenyl group (each isomer), propylphenyl group (each isomer ), butylphenyl group (each isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), undecylphenyl group (each isomer), dodecylphenyl group (each isomer), tridecylphenyl group (each isomer), tetradecylphenyl group (each isomer), methyl
  • Preferred hydroxy compounds (V) include aromatic hydroxy compounds represented by the following general formula (V-1) (hereinafter sometimes referred to as "aromatic hydroxy compounds (V-1)").
  • ring A 511 is an aromatic hydrocarbon ring having 6 to 20 carbon atoms;
  • R 511 is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 20 or less, an aryl group having 6 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aralkyloxy group having 7 to 20 carbon atoms, or hydroxy
  • R 511 may combine with Ring A 511 to form a ring structure, and n511 is an integer of 1 or more and 10 or less.
  • R511 Examples of the alkyl group having 1 to 20 carbon atoms in R 511 include methyl group, ethyl group, propyl group (each isomer), butyl group (each isomer), pentyl group (each isomer), hexyl group ( isomer), heptyl group (each isomer), octyl group (each isomer), nonyl group (each isomer), decyl group (each isomer), dodecyl group (each isomer), octadecyl group (each isomer) body) and the like.
  • the alkoxy group having 1 to 20 carbon atoms in R 511 includes, for example, methoxy group, ethoxy group, propoxy group (each isomer), butyloxy group (each isomer), pentyloxy group (each isomer), hexyloxy group (each isomer), heptyloxy group (each isomer), octyloxy group (each isomer), nonyloxy group (each isomer), decyloxy group (each isomer), dodecyloxy group (each isomer), octadecyloxy group (each isomer) and the like.
  • Examples of the aryl group having 6 to 20 carbon atoms in R 511 include a phenyl group and a naphthyl group.
  • Examples of the aryl group having an alkyl group as a substituent in R 511 include a methylphenyl group (each isomer), an ethylphenyl group (each isomer), a propylphenyl group (each isomer), a butylphenyl group (each isomer isomer), pentylphenyl group (each isomer), hexylphenyl group (each isomer), heptylphenyl group (each isomer), octylphenyl group (each isomer), nonylphenyl group (each isomer), decylphenyl group (each isomer), biphenyl group (each isomer), dimethylphenyl group (each isomer), diethylphenyl group (each isomer), dipropylphenyl group (each isomer), dibutylphenyl group (each isomer ),
  • Examples of the aryloxy group having 6 to 20 carbon atoms in R 511 include a phenoxy group, a methylphenoxy group (each isomer), an ethylphenoxy group (each isomer), a propylphenoxy group (each isomer), and a butylphenoxy group.
  • each isomer pentylphenoxy group (each isomer), hexylphenoxy group (each isomer), heptylphenoxy group (each isomer), octylphenoxy group (each isomer), nonylphenoxy group (each isomer ), decylphenoxy group (each isomer), phenylphenoxy group (each isomer), dimethylphenoxy group (each isomer), diethylphenoxy group (each isomer), dipropylphenoxy group (each isomer), dibutylphenoxy group (each isomer), dipentylphenoxy group (each isomer), dihexylphenoxy group (each isomer), diheptylphenoxy group (each isomer), diphenylphenoxy group (each isomer), trimethylphenoxy group (each isomer isomer), triethylphenoxy group (each isomer), tripropy
  • the aralkyl group having 7 to 20 carbon atoms in R 511 includes, for example, a phenylmethyl group, a phenylethyl group (each isomer), a phenylpropyl group (each isomer), a phenylbutyl group (each isomer), and phenylpentyl. group (each isomer), phenylhexyl group (each isomer), phenylheptyl group (each isomer), phenyloctyl group (each isomer), phenylnonyl group (each isomer), and the like.
  • the aralkyloxy group having 7 to 20 carbon atoms in R 511 includes, for example, a phenylmethoxy group, a phenylethoxy group (each isomer), a phenylpropyloxy group (each isomer), and a phenylbutyloxy group (each isomer). , phenylpentyloxy group (each isomer), phenylhexyloxy group (each isomer), phenylheptyloxy group (each isomer), phenyloctyloxy group (each isomer), phenylnonyloxy group (each isomer) etc.
  • Ring A 511 is an aromatic hydrocarbon ring having 6 to 20 carbon atoms. Ring A 511 may be monocyclic, polycyclic, or condensed. Specific examples of Ring A 511 include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthacene ring, chrysene ring, pyrene ring, triphenylene ring, pentalene ring, azulene ring, heptalene ring, indacene ring, biphenylene ring, and acenaphthylene. ring, aceanthrylene ring, acephenanthrylene ring, and the like.
  • ring A 511 is preferably a benzene ring, a naphthalene ring, or an anthracene ring, more preferably a benzene ring. These rings may also have substituents other than R 511 above. Substituents other than R 511 include the same as those exemplified for R 511 . R 511 and substituents other than R 511 consist of different functional groups.
  • n511 represents the number of substituents R511 and is an integer of 1 or more and 10 or less.
  • V-1 compounds in which ring A 511 is a benzene ring include, for example, compounds represented by the following general formula (V-1-1) (hereinafter referred to as "hydroxy compound (V-1-1 )”) and the like.
  • R 512 to R 516 are each independently the same as R 511 above.
  • At least one of R 512 to R 516 is preferably a hydrogen atom, and more preferably all of R 512 to R 516 are hydrogen atoms.
  • Preferred hydroxy compounds (V-1-1) include, for example, phenol, 2-ethylphenol, 2-propylphenol (each isomer), 2-butylphenol (each isomer), 2-pentylphenol (each isomer) , 2-hexylphenol (each isomer), 2-heptylphenol (each isomer), 2-phenylphenol, 2,6-dimethylphenol, 2,4-diethylphenol, 2,6-diethylphenol, 2,4 -dipropylphenol (each isomer), 2,6-dipropylphenol (each isomer), 2,4-dibutylphenol (each isomer), 2,4-dipentylphenol (each isomer), 2,4 -dihexylphenol (each isomer), 2,4-diheptylphenol (each isomer), 2-methyl-6-ethylphenol, 2-methyl-6-propylphenol (each isomer), 2-methyl-6 -butyl
  • the reaction liquid containing the isocyanate compound (II) is purified by distillation in the presence of the carbonyl compound (I), and the isocyanate compound (II) is continuously produced as a gas phase component. ).
  • the isocyanate compound (II) is obtained by thermally decomposing the carbamate compound (VI) in the presence of the carbonate ester (IV).
  • the isocyanate (II) is obtained by subjecting the carbamate compound (VI) to a thermal decomposition reaction in the presence of the carbonate ester (IV) as a solvent.
  • the thermal decomposition reaction side reactions represented by the above formulas (B) to (E) occur, and the resulting isocyanurate group, carbodiimide group, and allophanate group act as cross-linking points to produce high molecular weight components and solids. Refinement of the product and an increase in liquid viscosity may occur.
  • the carbonyl compound (I) acts as a good solvent for the above-described high molecular weight component, and the carbonyl compound (I) acts as a terminal blocker and acts as a side effect.
  • the carbonate (IV) may be supplied to the reactor before starting the reaction, may be supplied during the reaction, or both. Among them, it is preferable to supply to the reactor before the reaction.
  • the amount (molar amount) of the carbonate ester (IV) used as a solvent is preferably large from the viewpoint of suppressing side reactions.
  • the ratio is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and even more preferably 0.1 to 50 times.
  • the carbonate ester (IV) may be used as it is, or the carbonate ester (IV) may be newly added to the carbamate. It may be added to compound (VI).
  • the reaction temperature is usually 100° C. or higher and 400° C. or lower, and a high temperature is preferable in order to increase the reaction rate. Since the above-mentioned compounds may cause side reactions as described above, the temperature is preferably 130° C. or higher and 300° C. or lower, more preferably 150° C. or higher and 280° C. or lower. In order to keep the reaction temperature constant, a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually carried out in the range of 20 Pa or more and 1 ⁇ 10 6 Pa or less.
  • reaction time is not particularly limited, and is usually 0.001 hours or more and 100 hours or less, preferably 0.01 hours or more and 50 hours or less, and 0.1 hours or more and 10 hours or less. more preferred.
  • a catalyst can be used, and the amount of the catalyst used is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.5% by mass or more and 20% by mass or less, relative to the mass of the carbamate compound.
  • catalysts include organometallic catalysts such as dibutyltin dilaurate, lead octylate and stannous octoate; and amines such as 1,4-diazabicyclo[2,2,2]octane, triethylenediamine and triethylamine. Even under the name k, organometallic catalysts such as dibutyltin dilaurate, lead octoate, stanaoctoate and the like are suitable. These compounds may be used alone or as a mixture of two or more.
  • the thermal decomposition reaction is a reaction that produces the corresponding isocyanate compound (II) and a hydroxy compound from the carbamate compound (VI), but the thermal decomposition reaction is an equilibrium reaction. Therefore, in order to efficiently obtain the isocyanate compound (II) in the thermal decomposition reaction, the hydroxy compound, which is the product of the thermal decomposition reaction, is removed from the thermal decomposition reaction system as a gas phase component by a method such as distillation. preferably taken out.
  • reaction liquid obtained in the thermal decomposition step contains the carbonyl compound (I)
  • the reaction liquid is referred to as a reaction liquid (isocyanate composition) containing the isocyanate compound (II) and the carbonyl compound (I), which will be described later. You may use it for the refinement
  • the carbonyl compound (I) obtained by the “method for producing a carbonyl compound” may be mixed with a reaction solution containing an isocyanate compound (isocyanate composition), and used in the purification step described later.
  • the composition of the isocyanate composition is ⁇ 3 x (molar amount of isocyanurate group) + 2 x (molar amount of carbodiimide group) + 3 x (uretonimine group) from the viewpoint of ensuring good distillation operability in the purification step described later.
  • (molar amount) + 2 ⁇ (molar amount of allophanate 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 0 It is more preferably 0.001 or more and 8.0 or less.
  • the isocyanate compound is purified from the isocyanate composition described above. Specifically, in the purification step, first, components having a boiling point lower than that of the isocyanate compound contained in the isocyanate composition (low-boiling component) are distilled off (hereinafter referred to as “light-boiling separation”), and then the isocyanate compound is is recovered as a gas phase component and separated from components (high-boiling components) having a higher boiling point than the isocyanate compound (hereinafter referred to as "high-boiling separation”) to purify the isocyanate compound from the isocyanate composition.
  • low-boiling component components having a boiling point lower than that of the isocyanate compound contained in the isocyanate composition
  • low-boiling separation components having a boiling point lower than that of the isocyanate compound contained in the isocyanate composition
  • high-boiling separation components having a higher boiling point than the isocyanate compound having a
  • the distillation method is not particularly limited as long as the light-boiling components can be separated as gas phase components.
  • the term "low-boiling component (low-boiling point component)" as used herein refers to a component with a boiling point lower than that of a carbonyl compound. , and a hydroxy compound that is a by-product of a thermal decomposition reaction.
  • the pressure for distilling off the low-boiling components varies depending on the type of compound and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure as long as the isocyanate compound and the low-boiling components can be separated. , 20 Pa or more and 1 ⁇ 10 6 Pa or less is preferable, 20 Pa or more and 1 ⁇ 10 4 Pa or less is more preferable, 20 Pa or more and 1 ⁇ 10 3 Pa or less is more preferable, and 20 Pa or more and 1 ⁇ 10 2 Pa or less is particularly preferable.
  • the operation time (residence time in the case of a continuous method) when distilling off the low-boiling component is not particularly limited as long as the isocyanate compound and the low-boiling component can be separated, and side reactions with the isocyanate compound are suppressed. From the viewpoint, it is preferably 5 seconds or more and 100 hours or less, more preferably 10 seconds or more and 50 hours or less, and even more preferably 20 seconds or more and 10 hours or less.
  • the temperature at which the low-boiling component is distilled off is not particularly limited as long as the isocyanate compound is stable and the isocyanate compound and the low-boiling component can be separated. 300° C. or higher is preferable, 30° C. or higher and 280° C. or lower is more preferable, and 40° C. or higher and 250° C. or lower is even more preferable.
  • the distillation method is not particularly limited as long as the isocyanate can be separated as a gas phase component.
  • high-boiling component high-boiling point component
  • the term "high-boiling point component" as used herein refers to a component with a boiling point higher than that of isocyanate.
  • carbamate compound (III) (carbate group-containing isocyanate) and carbamate compound (VI) (carbamate compound used as raw material for thermal decomposition step)
  • some isocyanate groups of the isocyanate compound are isocyanurate group, carbodiimide group, uretonimine group, and It is a compound converted into at least one functional group selected from the group consisting of allophanate groups (hereinafter referred to as "isocyanate polymer").
  • uretonimine groups by-produced in the thermal decomposition step or the low-boiling separation step undergo a reaction to regenerate isocyanate groups and carbodiimide groups as shown in the following formula (J), so they are recovered in the gas phase.
  • the recovery rate of the isocyanate compound may exceed 100% by mass.
  • R m and R n are each independently a divalent or higher organic group.
  • the isocyanate compound is distilled off, and the high-boiling component is concentrated and solidified, which may make it difficult to continue operation. becomes difficult.
  • the isocyanate (isocyanate polymer) in which a part of the isocyanate group is converted to at least one functional group selected from the group consisting of an isocyanurate group, a carbodiimide group, a uretonimine group, and an allophanate group has a high molecular weight.
  • the carbodiimide group generated by the above formula (J) during high-boiling separation and the isocyanate group of the isocyanate polymer are combined to form a uretonimine group (reverse reaction of the above formula (J)), and the isocyanate polymers are combined It is caused by increasing the molecular weight by
  • the carbonyl compound (I) has a higher boiling point than the isocyanate compound and has fewer cross-linking points than the isocyanate polymer, so it works as a solvent in the high-boiling separation step.
  • it binds to carbodiimide groups to prevent isocyanate polymers from binding to each other and increasing the molecular weight.
  • the pressure for separating the high-boiling component varies depending on the type of compound and the reaction temperature, but may be reduced pressure, normal pressure, or increased pressure as long as the isocyanate compound and the low-boiling component can be separated. 0.1 Pa or more and 1 ⁇ 10 6 Pa or less is preferable, 1 Pa or more and 1 ⁇ 10 4 Pa or less is more preferable, and 5 Pa or more and 1 ⁇ 10 3 Pa or less is even more preferable.
  • the operation time (residence time in the case of a continuous method) when separating the high-boiling component is not particularly limited as long as the isocyanate compound and the low-boiling component can be separated, from the viewpoint of suppressing side reactions with the isocyanate compound. Therefore, it is preferably 5 seconds to 100 hours, more preferably 10 seconds to 50 hours, even more preferably 15 seconds to 10 hours, particularly preferably 20 seconds to 1 hour, and most preferably 25 seconds to 10 minutes. .
  • the temperature at which the high-boiling component is separated is not particularly limited as long as the isocyanate compound is stable and the isocyanate compound and the low-boiling component can be separated. 250° C. or lower is preferable, 30° C. or higher and 230° C. or lower is more preferable, and 40° C. or higher and 200° C. or lower is even more preferable.
  • the material of the reactor and lines in which the thermal decomposition process and the purification process are performed may be any known material as long as it does not adversely affect the carbamate compound, the hydroxy compound and isocyanate compound that are the products, and the carbonate ester that is the solvent.
  • SUS304, SUS316, SUS316L, etc. are inexpensive, they can be preferably used.
  • reactors there are no particular restrictions on the type of reactor, and known tank-like and tower-like reactors can be used.
  • the low-boiling mixture containing the hydroxy compounds produced is withdrawn from the reactor as gaseous components, and unreacted carbamate compounds and compounds not withdrawn as gaseous components are removed.
  • Preferably used is one equipped with a line for extracting part or all of the mixed liquid from the reactor in a liquid state.
  • Such reactors include, for example, stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tubular reactors, continuous multi-stage distillation columns, packed columns, thin film evaporators, and reactors having a support inside. , a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, a bubble column, and a combination thereof. .
  • a method using a stirring tank equipped with a distillation column or a multi-stage stirring tank is preferable, and the gas-liquid contact area that allows the low boiling point component to be quickly transferred to the gas phase. Large structures of are preferred.
  • the low-boiling components are extracted from the reactor as gaseous components, and part or all of the mixed liquid containing the compounds not extracted is extracted from the reactor in liquid form.
  • the reactor in liquid form Preferably used is one having a line for Such reactors include, for example, stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tubular reactors, continuous multi-stage distillation columns, packed columns, thin film evaporators, and reactors having a support inside. , a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, a bubble column, and a combination thereof. .
  • the isocyanate compound is extracted from the reactor as a gaseous component, and part or all of the mixture containing the unextracted compound is extracted from the reactor in liquid form.
  • a line for Such reactors include, for example, stirred tanks, multi-stage stirred tanks, distillation columns, multi-stage distillation columns, multi-tubular reactors, continuous multi-stage distillation columns, packed columns, thin film evaporators, and reactors having a support inside. , a forced circulation reactor, a falling film evaporator, a falling drop evaporator, a trickle phase reactor, a bubble column, and a combination thereof. .
  • the carbamate compound (VI) is as exemplified in the above "Method for producing carbonyl compound".
  • a method for producing the carbamate compound (VI) for example, a method of producing from a carbonic acid derivative and an amine compound, or a method of producing from a carbonic acid derivative, a hydroxy compound and an amine compound are preferred.
  • the same hydroxy compound as the above hydroxy compound (V) is preferably used as the starting material for producing the carbamate compound (VI).
  • Examples of carbonic acid derivatives include urea and carbonate esters.
  • the carbonate used as a raw material for producing the carbamate compound (VI) the same carbonate as the carbonate (IV) is preferably used.
  • the carbonic acid derivative is preferably urea, diphenyl carbonate, or dibutyl carbonate, and more preferably urea or diphenyl carbonate.
  • amine compound (VII) As the amine compound, for example, a compound represented by the following general formula (VII) (hereinafter sometimes referred to as "amine compound (VII)”) is preferably used.
  • R 71 is a divalent to tetravalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, which may have an ester group of 1 to 4 carbon atoms or a nitrogen atom, or 6 or more carbon atoms. It is preferably an aromatic hydrocarbon group having a valence of 20 or less and having a valence of 20 or more and 3 or less.
  • R 71 is preferably a group represented by any one of the above formulas (Ia-1) to (Ia-24), and is represented by the formulas (Ia-1), (Ia-2), ( A group represented by Ia-3), (Ia-14), (Ia-18), or (Ia-19) is more preferable.
  • n71 is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably an integer of 3 or more and 4 or less.
  • Preferred amine compounds (VII) include, for example, 4-aminomethyl-1,8-octanediamine, 4,4′-diaminodiphenylmethane, lysine ⁇ -aminoethyl ester, lysine methyl ester, 4,4′-methylenebis(cyclohexyl amine), 1,3-di(aminomethyl)cyclohexane, and the like.
  • the isocyanate composition of the present embodiment has, with respect to the total mass of the isocyanate composition, 97% by mass or more of an isocyanate compound; a carbonyl compound represented by the following general formula (I) of 2.0 ppm by mass or more and 1.0 ⁇ 10 4 ppm by mass or less (hereinafter sometimes referred to as “carbonyl compound (I)”); contains The isocyanate compound and the carbonyl compound are different compounds.
  • R 11 is a (n11+n12)-valent organic group
  • R 12 is a monovalent organic group.
  • n11 is an integer of 1 or more and 8 or less
  • n12 is 0 or more and 7 or less.
  • the sum of n11 and n12 is an integer of 2 or more and 8 or less.
  • the carbonyl compound (I) acts effectively during storage of the isocyanate composition, and has the effect of improving the stability of the isocyanate compound without coloring the isocyanate composition. It is presumed that the effect is exhibited by the carbonyl group of the carbonyl compound (I) having reactivity with water and oxygen and suppressing the modification reaction of the isocyanate compound caused by water and oxygen. In addition, since the carbonyl compound (I) has a large number of carbon-oxygen unsaturated bonds, it tends to exhibit the above effect more.
  • the lower limit of the content of the carbonyl compound (I) is 2.0 mass ppm, preferably 3.0 mass ppm, and 5.0 mass ppm with respect to the total mass of the isocyanate composition. and more preferably 10 ppm by mass.
  • the upper limit of the content of the carbonyl compound (I) is 1.0 ⁇ 10 4 mass ppm, preferably 3.0 ⁇ 10 3 mass ppm, relative to the total mass of the isocyanate composition, It is more preferably 1.0 ⁇ 10 3 ppm by mass.
  • the content of the carbonyl compound (I) is 2.0 ppm by mass or more and 1.0 ⁇ 10 4 ppm by mass or less, and 3.0 ppm by mass or more and 3.0 ⁇ It is preferably 10 3 mass ppm or less, more preferably 5.0 mass ppm or more and 1.0 ⁇ 10 3 mass ppm or less, and 10 mass ppm or more and 1.0 ⁇ 10 3 mass ppm or less. More preferred.
  • the content of the carbonyl compound (I) is at least the above lower limit, it is possible to suppress the modification reaction of the isocyanate compound. and maintain good appearance.
  • the content of the isocyanate compound is 97% by mass or more, preferably 98% by mass or more, more preferably 99% by mass or more, relative to the total mass of the isocyanate composition.
  • the content of the isocyanate compound is at least the above lower limit value, a composition containing a sufficient amount of the isocyanate compound, which is the target substance, can be obtained.
  • the upper limit is not particularly limited, it can be less than 100% by mass.
  • Carbonyl compound (I) is a compound represented by the following general formula (I).
  • R 11 is a (n11+n12)-valent organic group
  • R 12 is a monovalent organic group.
  • n11 is an integer of 1 or more and 8 or less
  • n12 is 0 or more and 7 or less.
  • the sum of n11 and n12 is an integer of 2 or more and 8 or less.
  • R 11 , R 12 are as described in ⁇ Carbonyl compound>> above.
  • n11 is an integer of 1 or more and 8 or less.
  • n12 represents the number of isocyanate groups and is an integer of 0 or more and 7 or less.
  • the sum of n11 and n12 (n11+n12) is an integer of 2 or more and 8 or less, preferably an integer of 2 or more and 6 or less, more preferably an integer of 2 or more and 5 or less, and still more preferably an integer of 3 or more and 4 or less.
  • the value of (n11+n12) increases, the number of cross-linking points (isocyanate groups) per carbonyl compound molecule increases, and the number of structures that contribute to coloration and prevention of isocyanate modification increases.
  • the crosslink density is increased, the curing time can be shortened, the hardness of the polymer can be improved, and coloration and modification of isocyanate can be suppressed.
  • the crosslink density is increased means that the average molecular chain length between the crosslink points is decreased.
  • the highly reactive isocyanate group is heated, a modification reaction occurs, which causes sticking or clogging of the device.
  • (n11+n12) is preferably 5 or less, and (n11+n12) is further preferably 4 or less.
  • Preferred carbonyl compounds (I) include, for example, compounds represented by the following formulas (I-1a) to (I-24b) (hereinafter sometimes referred to as "carbonyl compounds (I-1a)" and the like), and the like. mentioned. Incidentally, carbonyl compounds (I-1a) ⁇ (I-1c), carbonyl compounds (I-2a) ⁇ (I-2c), carbonyl compounds (I-3a) ⁇ (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), Carbonyl compounds (I-8a) ⁇ (I-8b), carbonyl compounds (I-9a) ⁇ (I-9b), carbonyl compounds (I-10a) ⁇ (I-10b), carbonyl compounds (I-11a) ⁇ (I-11b), carbonyl compounds (I-12a) to (I-12b),
  • the carbonyl compound (I) may be used alone or in combination of two or more.
  • each carbonyl compound (I) has the same effect of improving the stability of the isocyanate compound, so they can be mixed at any ratio and used.
  • isocyanate compound (II) a compound represented by the following general formula (II) (hereinafter sometimes referred to as "isocyanate compound (II)”) is preferably used.
  • R21 , n21" R 21 and n21 are as described in ⁇ Isocyanate compound> in ⁇ Method for producing carbonyl compound>> above.
  • Preferred isocyanate compounds (II) include, for example, 4-isocyanatomethyl-1,8-octamethylene diisocyanate (TTI), 2-isocyanatoethyl-2,6-diisocyanatohexanoate (LTI), lysine methyl Ester Diisocyanate (LDI), Diisocyanatopentane (PDI), Diisocyanatohexane (HDI), Methylenebis(cyclohexylisocyanate) (HMDI), 1,3-bis(isocyanatomethyl)cyclohexane (HXDI), 3-isocyanato methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), diisocyanatoxylene (XDI), diisocyanatodiphenylmethane (MDI), diisocyanatotoluene (TDI) and the like.
  • TTI 4-isocyanatomethyl-1,8-oc
  • the isocyanate composition of the present embodiment preferably further contains one or more compounds selected from the group consisting of carbamate compounds and carbonate esters, each at 2.0 ppm by mass or more and 1.0 ⁇ 10 4 ppm by mass or less. .
  • Carbamate compounds and carbonate esters also exhibit the same effects as the carbonyl compound (I) described above.
  • the lower limit of the content of each of the carbamate compound and the carbonate ester is preferably 2.0 ppm by mass, more preferably 3.0 ppm by mass, relative to the total mass of the isocyanate composition. 5.0 ppm by mass is more preferable, and 10 ppm by mass is particularly preferable.
  • the upper limit of the content of each of the carbamate compound and the carbonate ester is preferably 1.0 ⁇ 10 4 ppm by mass and preferably 3.0 ⁇ 10 3 ppm by mass with respect to the total mass of the isocyanate composition. is more preferable, and 1.0 ⁇ 10 3 ppm by mass is even more preferable. That is, the content of each of the carbamate compound and the carbonate ester is preferably 2.0 ppm by mass or more and 1.0 ⁇ 10 4 ppm by mass or less, and 3.0 ppm by mass or more, relative to the total mass of the isocyanate composition.
  • the lower limit of the total content of these compounds is, relative to the total mass of the isocyanate composition, It is preferably 2.0 mass ppm, more preferably 3.0 mass ppm, even more preferably 5.0 mass ppm, and particularly preferably 10 mass ppm.
  • the upper limit of the total content of these compounds is preferably 1.0 ⁇ 10 5 mass ppm, more preferably 1.0 ⁇ 10 4 mass ppm, relative to the total mass of the isocyanate composition.
  • the total content of the carbonyl compound (I), the carbamate compound and the carbonate ester is preferably 2.0 mass ppm or more and 1.0 ⁇ 105 mass ppm or less with respect to the total mass of the isocyanate composition, It is more preferably 3.0 mass ppm or more and 1.0 ⁇ 10 4 mass ppm or less, further preferably 5.0 mass ppm or more and 3.0 ⁇ 10 3 mass ppm or less, and 10 mass ppm or more and 1.0 mass ppm or less. It is particularly preferable to be 0 ⁇ 10 3 ppm by mass or less. When the total content of these compounds is at least the above lower limit, the modification reaction of the isocyanate compound can be further suppressed, while when it is at most the above upper limit, coloring caused by unsaturated bonds is further suppressed. and maintain a better appearance.
  • carbamate compound (III) a compound represented by the following general formula (III) (hereinafter sometimes referred to as “carbamate compound (III)”) is preferably used.
  • n31 is an integer of 1 or more and 8 or less
  • n32 is an integer of 0 or more and 7 or less
  • the sum of n31 and n32 is an integer of 2 or more and 8 or less
  • n31+n32 n11+n12.
  • R 31 , R 31 , n31, n32 are as described in [Carbamate compound (III)] of ⁇ Production method of carbonyl compound>> above.
  • Preferred carbamate compounds (III) include, for example, compounds represented by the following formulas (III-1a) to (III-24b).
  • Each can be
  • carbamate compound (III) may be used alone or in combination of two or more.
  • the effect of improving the stability of the isocyanate compound by each carbamate compound (III) is the same, so they can be used by mixing at any ratio.
  • Carbonate ester a compound represented by the following general formula (IV) (hereinafter sometimes referred to as “carbonate ester (IV)”) is preferably used.
  • R41 and R42 are as described in ⁇ Carbonate ester> in ⁇ Production method of carbonyl compound>> above.
  • Preferred carbonate esters (IV) include, for example, diphenyl carbonate, bis(2-methoxyphenyl) carbonate, bis(2-ethoxyphenyl) carbonate and the like.
  • the isocyanate composition of the present embodiment contains 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 ester so as to have the above content. can be produced by mixing
  • composition containing the isocyanate compound (II) obtained by thermally decomposing a carbamate compound represented by the following general formula (VI) (hereinafter sometimes referred to as “carbamate compound (VI)”) is prepared in the present practice. It can also be used as an isocyanate composition in the form of
  • the composition containing the isocyanate compound (II) is obtained by thermally decomposing the carbamate compound (VI) in the presence of the carbonate ester (IV) as a solvent.
  • a hydroxy compound is produced as a by-product, it is preferable to proceed with the thermal decomposition reaction while extracting and separating the hydroxy compound.
  • a reaction solution containing carbamate compound (VI) is continuously supplied to a reactor to carry out a thermal decomposition reaction of carbamate compound (VI), and a by-produced hydroxy compound is continuously discharged from the reactor. It is a method of extracting effectively.
  • the thermal decomposition temperature varies depending on the type of carbamate compound (VI) used, but can be, for example, 140° C. or higher and 380° C. or lower.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, and may be any of reduced pressure, normal pressure, and increased pressure.
  • the pressure can be set to the saturated vapor pressure of the aprotic solvent used, and is preferably in the range of 20 Pa or more and 10 ⁇ 10 6 Pa or less.
  • the reaction time (residence time in the case of a continuous method) is not particularly limited, and can be 0.001 hour or more and 100 hours or less.
  • the above carbonyl compound (I) is presumed to be a reaction product of isocyanate compound (II) and carbonate ester (IV), and is considered to be produced under thermal decomposition reaction conditions. Therefore, the isocyanate composition obtained in the thermal decomposition reaction of carbamate compound (VI) contains a specific amount of carbonyl compound (I).
  • the carbamate compound (III) can also be said to be a reaction intermediate generated from the carbamate compound (VI) before becoming the final product, the isocyanate compound (II).
  • the isocyanate compound (II) By stopping the reaction when the content of the isocyanate compound (II) reaches a specific amount or more, an isocyanate composition containing the carbamate compound (III), which is the reaction intermediate, can be obtained.
  • the isocyanate composition obtained in the thermal decomposition reaction of the carbamate compound (VI) contains the carbonate ester (IV) as a solvent.
  • the carbonate (IV) can be separated from the isocyanate composition such that the content of the carbonate (IV) in the isocyanate composition is within a specified range.
  • the isocyanate compound, the carbonyl compound (I), and, if necessary, one or more compounds selected from the group consisting of carbamate compounds and carbonate esters are mixed so as to have the above-mentioned content, and the present embodiment
  • the carbonyl compound, carbamate compound, and carbonate ester can be produced by the methods shown below.
  • the isocyanate compound the one obtained by thermally decomposing the carbamate compound (VI) can be used after being purified as necessary.
  • Carbonyl compound (I) is a mixture of isocyanate compound (II) and carbonate ester (IV), or a mixture of carbamate compound (III) or carbamate compound (VI) and carbonate ester (IV), or isocyanate compound (II). , carbamate compound (III) or carbamate compound (VI), carbonate ester (IV), and a mixture of hydroxy compounds (these mixtures may hereinafter be referred to as "raw material mixture of carbonyl compound (I)"). By doing so, it is obtained.
  • Examples of the hydroxy compound used herein include the same hydroxy compounds that are by-produced in the thermal decomposition reaction of the carbamate compound (VI), and the details will be described later.
  • the amount (molar amount) of the carbonate ester (IV) used it is preferable to use a large amount of the carbonate solvent from the viewpoint of suppressing side reactions.
  • the stoichiometric ratio of the total molar amount of the carbamate compound (VI) and the isocyanate compound (II) is preferably 0.001 to 100 times, more preferably 0.01 to 80 times, and 0 .1 times or more and 50 times or less are more preferable.
  • the reaction temperature is usually 100° C. or higher and 400° C. or lower, and a high temperature is preferable in order to increase the reaction rate. 130° C. or higher and 300° C. or lower is preferable, and 150° C. or higher and 280° C. or lower is more preferable.
  • a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually carried out in the range of 20 Pa or more and 1 ⁇ 10 6 Pa or less.
  • reaction time is not particularly limited, and is usually 0.001 hours or more and 100 hours or less, preferably 0.01 hours or more and 50 hours or less, and 0.1 hours or more and 10 hours or less. more preferred.
  • the rate and amount of carbonyl compounds produced can be increased by heating the raw material liquid in contact with stainless steel.
  • stainless steel SUS316 or SUS304 can be used regardless of the shape, and for example, fillers and metal pieces are preferably used.
  • the packing is not particularly limited, but DIXON Packing, McMAHON Packing, Coil PACK, MESH RING, CANNON Packing, HELI PACK, RASCHIG RING, PRICKLE RING, etc. are used.
  • the volume of the raw material liquid of the carbonyl compound is V and the surface area of the stainless steel is A
  • the larger the contact area with the stainless steel per unit volume of the raw material liquid the more the value of the carbonyl compound generation rate A/V is 0.001 m 2 . /m 3 or more and 100,000 m 2 /m 3 or less is preferable, 0.01 m 2 /m 3 or more and 50,000 m 2 /m 3 or less is more preferable, and 0.1 m 2 /m 3 or more and 10,000 m 2 /m 3 or less is even more preferable.
  • reaction format is not particularly limited, a reactor capable of efficiently mixing the raw material mixture of the carbonyl compound (I), or the raw material mixture of the carbonyl compound (I) and stainless steel, and heating the reactor is preferable, such as a stainless steel stirring tank or distillation column. A method of heating the raw material liquid at is preferred.
  • the low-boiling component of the liquid after heating the raw material mixture of carbonyl compound (I) may be distilled off, and the distillation method is not particularly limited as long as the low-boiling component can be separated as a gas phase component.
  • a low-boiling component refers to a component having a boiling point lower than that of the carbonyl compound (I), and varies depending on the substance used, but is mainly a group consisting of the carbonate ester (IV), the isocyanate compound (II), and the hydroxy compound. It is one or more compounds selected from
  • the carbamate compound (III) is obtained by mixing and heating the isocyanate compound (II) and the hydroxy compound represented by the formula (V) (hereinafter sometimes referred to as "hydroxy compound (V)"). and a method of thermally decomposing the carbamate compound represented by the formula (VI).
  • the mixing ratio of the isocyanate group of the isocyanate compound (II) to the hydroxyl group of the hydroxy compound (V) is NCO:OH is (n31+n32): Mixing and heating to n31 is preferred.
  • the reaction temperature is usually 40° C. or higher and 400° C. or lower, and a high temperature is preferable in order to increase the reaction rate. 80° C. or higher and 300° C. or lower is preferable, and 100° C. or higher and 250° C. or lower is more preferable.
  • a known cooling device or heating device may be installed in the reactor.
  • the reaction pressure varies depending on the type of compound used and the reaction temperature, but may be any of reduced pressure, normal pressure, and increased pressure, and is usually carried out in the range of 20 Pa or more and 1 ⁇ 10 6 Pa or less.
  • reaction time is not particularly limited, and is usually 0.001 hours or more and 100 hours or less, preferably 0.01 hours or more and 50 hours or less, and 0.1 hours or more and 10 hours or less. more preferred.
  • the carbonate ester (IV) can be synthesized, for example, using the methods described in Japanese Patent No. 3071008 (Reference 1) and Japanese Patent No. 4137941 (Reference 2). Specifically, the carbonate ester (IV) is obtained by reacting an aromatic monohydroxy compound with phosgene or a chlorocarbonate of an aromatic monohydroxy compound in the presence of activated carbon while eliminating hydrogen chloride, or Step (1) of reacting an organometallic compound with carbon dioxide to obtain a reaction mixture containing the dialkyl carbonate formed in the reaction; Step (2) of separating the dialkyl carbonate from the reaction mixture to obtain a residual liquid.
  • steps (3) and (4) above can be performed directly or in reverse order, or partially or wholly simultaneously.
  • the isocyanate composition of the present embodiment is sufficiently suppressed in coloration and has excellent storage stability, for example, curing in fields where appearance quality is required, such as baking paints, automobile clear coating materials, and coil coating materials. It is suitably used as a raw material for a drug.
  • Step (1-1) Production Step of Carbamate Compound A reaction was carried out using the apparatus shown in FIG.
  • the apparatus shown in FIG. 1 was also used in the production of carbamate compounds in Example 1-1 and later.
  • With the line 14 closed 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine was supplied from the storage tank 101 through the line 11 to the baffled SUS reaction vessel 104.
  • 50 kg (58.5 mol) was supplied from the storage tank 102 through the line 12 to the reaction vessel 104 and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 15.53 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (1-1) As a result of analyzing the solution after the reaction (hereinafter referred to as “reaction solution (1-1)”) by liquid chromatography, the yield of the carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was 99% by mass. was generated in The line 16 was opened, and the above reaction solution (1-1) was transferred to the storage tank 106 via the line 16 . The mass of the reaction liquid (1-1) was 19.40 kg.
  • the apparatus shown in FIG. 2 was also used for the thermal decomposition of carbamate compounds in Example 1-1 and later.
  • the temperature of the multistage distillation column 203 was raised to 170° C.
  • the jacket temperature of the reaction vessel 201 was heated to 228° C.
  • the pressure was reduced to 14 kPa.
  • 19.40 kg of the reaction liquid (1-1) collected in the storage tank 106 in the step (1-1) is heated to 120° C.
  • reaction solution (1-2) was purified with a column fractionator to isolate the carbonyl compound.
  • the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-1a) to (I-1c). Also, FIG. 5 shows the 1 H-NMR spectrum of the carbonyl compound.
  • TTI was produced at a yield of 70% by mass.
  • the value of (molar amount of group)+3.times.(molar amount of uretonimine group)+2.times.(molar amount of allophanate group) ⁇ /(molar amount of carbonyl compound) was 3.7.
  • the apparatus shown in FIG. 3 was also used in the low boiling point separation in Example 1-1 and later.
  • the reaction liquid (1-2) was continuously fed at 3.73 kg/hour from the storage tank 205 to the middle stage of the continuous multi-stage distillation column 301 through the line 31, and the liquid phase component was separated by distillation.
  • the amount of heat required for the distillation separation was supplied by circulating the liquid at the bottom of the column through reboiler A32 and line 33.
  • the liquid temperature at the bottom of the continuous multi-stage distillation column was 220°C, and the pressure at the top was 1.5 kPa.
  • reaction liquid (1-3) The liquid collected in the storage tank 303 (hereinafter referred to as "reaction liquid (1-3)") weighed 7.45 kg, and was analyzed by NMR, LC, and gas chromatography, and was found to be the supplied reaction liquid (1-2).
  • TTI was recovered with a yield of 82% by mass, and the reaction solution at this time was ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group )+2 ⁇ (molar amount of allophanate group) ⁇ (molar amount of carbonyl compound) was 4.6.
  • the apparatus shown in FIG. 4 was also used in the high boiling point separation in Example 1-1 and later.
  • a thin film distillation apparatus 401 manufactured by Kobelco Eco-Solutions Co., Ltd., Japan
  • the reaction liquid (1-3) recovered in the storage tank 303 in the step (1-3) is supplied to the upper part of the thin film distillation apparatus 401 at about 1.0 kg/hour through the line 41 to separate the isocyanate and the high-boiling components. gone.
  • the produced gaseous phase component was transferred to storage tank 402 via line 42 and condenser (condenser) A41.
  • the liquid recovered from the storage tank 402 was 3.35 kg, and the recovery rate of TTI was 121% by mass. The reason why the TTI recovery rate exceeds 100% by mass is that part of the isocyanate-modified product produced in the thermal decomposition step or the low boiling point separation step is regenerated into TTI.
  • reaction solution (2-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (2-2)”) by NMR, LC, and gas chromatography showed that TTI was produced in a yield of 78% by mass.
  • reaction solution (2-2) ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 4.3.
  • Step (2-3) Low boiling point separation step
  • the reaction liquid (2-2) is continuously fed at 4.19 kg/hour, except that the withdrawal rate in the steady state of the line 34 is 1.26 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 is 6.29 kg, and as a result of analysis by NMR, LC, and gas chromatography, TTI was collected with a yield of 77% by mass with respect to the supplied reaction liquid (2-2).
  • the liquid recovered in the storage tank 402 was 3.36 kg, and the recovery rate of TTI was 116% by mass.
  • reaction solution (3-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (3-2)”) by NMR, LC, and gas chromatography showed that TTI was produced in a yield of 73% by mass.
  • reaction solution (3-2) ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 3.9.
  • Step (3-3) Low boiling point separation step
  • the reaction liquid (3-2) is continuously fed at 4.42 kg/hour, and the withdrawal rate in the steady state of the line 34 is 1.42 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the amount of the liquid recovered in the storage tank 303 was 7.08 kg, and as a result of analysis by NMR, LC, and gas chromatography, TTI was recovered with a yield of 80% by mass with respect to the supplied reaction liquid (3-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 5.5.
  • Step (3-4) High boiling point separation step High boiling point separation was performed in the same manner as in Example 1-1, except that the liquid collected in the storage tank 303 in step (3-3) was used.
  • the liquid recovered in the storage tank 402 was 3.35 kg, and the recovery rate of TTI was 119% by mass.
  • reaction solution (4-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (4-2)”) by NMR, LC, and gas chromatography showed that TTI was produced in a yield of 79% by mass.
  • reaction solution (4-2) ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 1.6.
  • Step (4-3) Low boiling point separation step
  • the reaction liquid (4-2) is continuously fed at 4.42 kg/hour, and the withdrawal rate in the steady state of the line 34 is 1.68 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 8.41 kg, and as a result of analysis by NMR, LC, and gas chromatography, TTI was collected with a yield of 85% by mass with respect to the supplied reaction liquid (4-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.6.
  • Step (4-4) High boiling point separation step High boiling point separation was performed in the same manner as in Example 1-1, except that the liquid recovered in the storage tank 303 in step (4-3) was used.
  • the liquid recovered in the storage tank 402 was 4.05 kg, and the recovery rate of TTI was 125% by mass.
  • Step (5-1) Carbamate Compound Production Step 0.23 kg (69.2 mol) of urea was used instead of diphenyl carbonate, 25.87 kg (275.2 mol) of phenol was supplied to storage tank 102, A carbamate was synthesized in the same manner as in Example 1-1, except that the reaction temperature was changed to 240° C. and the mixture was stirred for 30 minutes. The amount of phenol and ammonia withdrawn into the storage tank 107 was 24.14 kg.
  • reaction solution (5-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction solution (5-1)") by liquid chromatography, the corresponding carbamate compound was produced with a yield of 99% by mass.
  • Line 16 was opened, and the reaction solution (5-1) was transferred to storage tank 106 via line 16 .
  • the mass of the reaction liquid (5-1) was 10.79 kg.
  • reaction solution (5-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (5-2)”) by NMR, LC, and gas chromatography showed that TTI was produced in a yield of 78% by mass.
  • reaction solution (5-2) ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 1.5.
  • Step (5-3) Low boiling point separation step
  • the reaction liquid (5-2) is continuously fed at 4.27 kg/hour, except that the withdrawal rate in the steady state of the line 34 is 1.75 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 8.75 kg, and as a result of analysis by NMR, LC, and gas chromatography, TTI was collected with a yield of 84% by mass with respect to the supplied reaction liquid (5-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.5.
  • Step (5-4) High boiling point separation step High boiling point separation was performed in the same manner as in Example 1-1, except that the liquid recovered in the storage tank 303 in step (5-3) was used.
  • the liquid recovered in the storage tank 402 was 4.05 kg, and the recovery rate of TTI was 128% by mass.
  • Step (6-1) Carbamate Compound Production Step Instead of phenol, 12.40 kg (58.5 mol) of 4-cumylphenol was supplied to the baffled SUS reactor 104, and 4-cumylphenol was added instead of phenol. Carbamate synthesis was carried out in the same manner as in Example 1-5, except that 18.97 kg (89.47 mol) was supplied to the baffled SUS reactor 105. The amount of 4-cumylphenol and ammonia discharged into the storage tank 107 was 16.97 kg.
  • reaction liquid (6-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (6-1)") by liquid chromatography, the corresponding carbamate compound was produced with a yield of 99% by mass.
  • the line 16 was opened, and the reaction solution (6-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (6-1) was 17.96 kg.
  • reaction solution (6-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (6-2)”) by NMR, LC, and gas chromatography showed that TTI was produced in a yield of 75% by mass.
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 1.4.
  • a carbonyl compound was isolated by purifying a portion of the reaction solution (6-2) with a column preparative device. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-3a) to (I-3c).
  • the reaction liquid (6-2) is continuously fed at 16.10 kg/hour, and the withdrawal rate in line 34 in a steady state is 15.77 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 31.55 kg, and as a result of analysis by NMR, LC, and gas chromatography, TTI was collected with a yield of 95% by mass with respect to the supplied reaction liquid (6-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 1.6.
  • the liquid recovered in the storage tank 402 was 4.19 kg, and the recovery rate of TTI was 122% by mass.
  • Step (1′-2) Thermal decomposition step of carbamate compound 19.4 kg of the reaction solution (1-1) of Example 1-1 and barrel process oil B-03 (benzyl toluene, Matsumura Oil Co., Ltd.) were added to 5. Using 45 kg, the reaction liquid (1-1) was supplied to the reactor over about 14 minutes to start the reaction, the jacket temperature was 238 ° C., the internal temperature was 230 ° C., the reflux ratio was 1.5, and the pressure was 25 to 35 kPa. A thermal decomposition reaction was carried out in the same manner as in Example 1-1, except that the reaction was carried out within the range and the extraction of phenol was continued for 1.5 hours after the reaction liquid (1-1) was completely transferred.
  • barrel process oil B-03 benzyl toluene, Matsumura Oil Co., Ltd.
  • reaction solution (1′-2) The mass of the reaction liquid transferred to the storage tank 205 was 5.71 kg. Analysis of this reaction solution (hereinafter referred to as “reaction solution (1′-2)”) by NMR, LC, and gas chromatography revealed that TTI was produced with a yield of 69% by mass. No carbonyl compound was produced in the reaction solution at this time, and by-products having isocyanurate groups, carbodiimide groups, uretonimine groups and allophanate groups were found.
  • Step (1′-3) Low boiling point separation step
  • the reaction liquid (1′-2) is continuously fed at 4.35 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.74 kg/hour. Except for this, when low boiling point separation was carried out in the same manner as in Example 1-1, the liquid became highly viscous during operation, making it difficult to continue operation.
  • Step (7-1) Production Step of Carbamate Compound A reaction was carried out using the apparatus shown in FIG. With the line 14 closed, 3.33 kg (16.8 mol) of 4,4'-diaminodiphenylmethane was supplied from the storage tank 101 through the line 11 to the baffled SUS reaction vessel 104, and 2.53 kg (27.8 mol) of phenol was added. 0 mol) was supplied from the storage tank 102 to the reaction vessel 104 through the line 12, and was homogenized by stirring.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 7.58 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (7-1) a carbamate compound corresponding to 4,4′-diaminodiphenylmethane was produced with a yield of 95% by mass. rice field.
  • Line 16 was opened, and the reaction solution (7-1) was transferred to storage tank 106 via line 16 .
  • the mass of the reaction liquid (7-1) was 12.77 kg.
  • Step (7-2) Thermal Decomposition Step of Carbamate Compound Using 12.77 kg of reaction liquid (7-1) and 12.77 kg of diphenyl carbonate, reaction liquid (7-1) was added to the reactor over about 10 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 0.8, and a pressure of 11 to 16 kPa. A pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 11.75 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (7-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-2).
  • Step (7-3) Low boiling point separation step
  • the reaction liquid (7-2) is continuously fed at 2.35 kg/hour, except that the withdrawal rate in the steady state of the line 34 is 1.97 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 9.87 kg, and as a result of analysis by NMR, LC, and gas chromatography, MDI was collected with a yield of 79% by mass with respect to the supplied reaction liquid (7-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.3.
  • Step (7-4) High boiling point separation step Example 1-1 except that the liquid recovered in the storage tank 303 in the step (7-3) was used, the operating temperature was 170 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 4.54 kg, and the recovery rate of MDI was 130% by mass.
  • Step (8-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (16.8 mol) of lysine ⁇ -aminoethyl ester trihydrochloride is transferred from the storage tank 101 through the line 11 to a baffled SUS Then, 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12, and stirred to homogenize. Next, with the line 16 closed, 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 11.91 kg (55.6 mol) of diphenyl carbonate was added.
  • reaction solution (8-1) Liquid chromatography analysis of the solution after the reaction (hereinafter referred to as “reaction solution (8-1)”) revealed that a carbamate compound corresponding to lysine ⁇ -aminoethyl ester was produced at a yield of 96% by mass. .
  • the line 16 was opened and the above reaction liquid (8-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (8-1) was 11.45 kg.
  • Step (8-2) Thermal Decomposition Step of Carbamate Compound Using 11.45 kg of reaction liquid (8-1) and 10.00 kg of diphenyl carbonate, reaction liquid (8-1) was added to the reactor over about 15 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 3.2, and a pressure of 11 to 16 kPa. A pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of was continued. The mass of the reaction liquid transferred to the storage tank 205 (hereinafter referred to as "reaction liquid (8-2)”) was 9.01 kg.
  • FIGS. 6A and 6B The results of 1 H-NMR and gas chromatography-mass spectrometry of the reaction solution (8-2) are shown in FIGS. 6A and 6B, respectively. Further, a carbonyl compound was isolated by purifying a portion of the reaction solution (8-2) with a column preparative device. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-4a) to (I-4c).
  • Step (8-3) Low boiling point separation step
  • the reaction liquid (8-2) is continuously fed at 1.80 kg/hour, except that the withdrawal rate in the steady state of the line 34 is 1.10 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1. 5.50 kg of the liquid collected in the storage tank 303 was analyzed by NMR, LC, and gas chromatography, and LTI was collected with a yield of 83% by mass with respect to the supplied reaction liquid (8-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.4.
  • Step (8-4) High boiling point separation step Example 1-1 except that the liquid recovered in the storage tank 303 in the step (8-3) was used, the operating temperature was 190 ° C., and the internal pressure was 0.1 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 2.38 kg, and the recovery rate of LTI was 125% by mass.
  • Step (9-1) Carbamate Compound Production Step Instead of phenol, 0.84 kg (6.75 mol) of 2-methoxyphenol was supplied to the baffled SUS reactor 104, and 0.84 kg (6.75 mol) of 2-methoxyphenol was added instead of phenol. Same as Example 1-8, except that 84 kg (6.75 mol) was supplied to the baffled SUS reactor 105 with 15.26 kg (55.6 mol) of bis(2-methoxyphenyl) carbonate instead of diphenyl carbonate. Carbamate synthesis was carried out by the procedure of . The amount of 2-methoxyphenol withdrawn into the storage tank 107 was 6.35 kg.
  • reaction liquid (9-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (9-1)") by liquid chromatography, the corresponding carbamate compound was produced with a yield of 98% by mass.
  • Line 16 was opened, and the reaction solution (9-1) was transferred to storage tank 106 via line 16 .
  • the mass of the reaction liquid (9-1) was 13.95 kg.
  • Step (9-2) Thermal Decomposition Step of Carbamate Compound Using 14.0 kg of reaction solution (9-1) and 8.0 kg of bis(2-methoxyphenyl)carbonate, about 14 kg of reaction solution (9-1) was used. The reaction was started by supplying the reaction mixture to the reactor over a period of minutes, and the reaction was performed at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 3.0, and a pressure of 8 to 13 kPa. A pyrolysis reaction was carried out in the same manner as in Example 1-8, except that extraction of 2-methoxyphenol was continued for 3 hours after transfer. The mass of the reaction liquid transferred to the storage tank 205 was 12.05 kg.
  • reaction solution (9-2) Analysis of this reaction solution (hereinafter referred to as "reaction solution (9-2)") by NMR, LC, and gas chromatography showed that LTI was produced in a yield of 78% by mass.
  • a carbonyl compound was isolated by purifying a portion of the reaction solution (9-2) with a column preparative device. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-5a) to (I-5c).
  • Step (9-3) Low boiling point separation step
  • the reaction liquid (9-2) was continuously fed at a pressure of 1.0 kPa at a rate of 2.41 kg/hour, and the withdrawal rate in line 34 in a steady state was 1.0 kPa.
  • Light boiling separation was performed in the same manner as in Example 1-1 except that the rate was 16 kg/hour.
  • the liquid collected in the storage tank 303 was 5.79 kg, and as a result of analysis by NMR, LC, and gas chromatography, LTI was collected with a yield of 85% by mass with respect to the supplied reaction liquid (9-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.2.
  • Step (9-4) High boiling point separation step High boiling point separation was performed in the same manner as in Example 1-1 except that the liquid collected in the storage tank 303 in step (9-3) was used.
  • the liquid collected in the storage tank 402 was 2.43 kg, and the recovery rate of LTI was 123% by mass.
  • Step (10-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride is transferred from the storage tank 101 through the line 11 into the baffled SUS reaction vessel 104. , 1.91 kg (20.3 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12 and stirred to homogenize. Next, with the line 16 closed, 1.91 kg (20.3 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 10.17 kg (47.5 mol) of diphenyl carbonate was added. was supplied from the storage tank 103 to the reaction vessel 105 through the line 13 .
  • reaction solution (10-1) a carbamate compound corresponding to lysine methyl ester was produced with a yield of 97% by mass.
  • the line 16 was opened and the above reaction liquid (10-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (10-1) was 11.38 kg.
  • Step (10-2) Thermal Decomposition Step of Carbamate Compound Using 11.38 kg of reaction liquid (10-1) and 11.38 kg of diphenyl carbonate, reaction liquid (10-1) was added to the reactor over about 12 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 0.9, and a pressure of 20 to 29 kPa. A pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 19.35 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (10-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-7a) to (I-7b).
  • LC calibration curve was created from the obtained carbonyl compounds, and the carbonyl compounds were quantified by the absolute calibration curve method. Further, as a result of analysis by NMR and gas chromatography, lysine diisocyanate (LDI) was produced with a yield of 81% by mass. ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (molar amount of allophanate group) of the reaction solution at this time molar amount) value was 1.4.
  • Step (10-3) Low boiling point separation step
  • the reaction liquid (10-2) is continuously fed at 3.87 kg/hour, except that the withdrawal rate in the steady state of line 34 is 1.47 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 7.35 kg, and as a result of analysis by NMR, LC, and gas chromatography, LDI was collected with a yield of 86% by mass with respect to the supplied reaction liquid (10-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 2.5.
  • Step (10-4) High boiling point separation step Example 1-1 except that the liquid recovered in the storage tank 303 in the step (10-3) was used, the operating temperature was 180 ° C., and the internal pressure was 0.1 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 4.57 kg, and the recovery rate of LDI was 122% by mass.
  • Step (11-1) Carbamate Compound Production Step Instead of lysine methyl ester dihydrochloride, 3.33 kg (13.5 mol) of lysine ethyl ester dihydrochloride and 1.70 kg (18.04 mol) of phenol were added to a baffled SUS. The same as in Example 1-10 except that 1.70 kg (18.04 mol) of phenol and 9.59 kg (44.81 mol) of diphenyl carbonate were supplied to the baffled SUS reactor 105. Carbamate synthesis was carried out by the procedure of . The amount of phenol drawn out to the storage tank 107 was 5.59 kg.
  • reaction liquid (11-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (11-1)") by liquid chromatography, the corresponding carbamate compound was produced with a yield of 97% by mass.
  • the line 16 was opened, and the reaction liquid (11-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (11-1) was 10.74 kg.
  • reaction solution (11-2) Analysis of this reaction solution (hereinafter referred to as “reaction solution (11-2)”) by NMR, LC, and gas chromatography showed that LDI-Et was produced with a yield of 82% by mass.
  • a carbonyl compound was isolated by purifying a portion of the reaction solution (11-2) with a column preparative device. The isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-10a) to (I-10b).
  • the reaction liquid (11-2) is continuously fed at 3.65 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.31 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 6.57 kg, and as a result of analysis by NMR, LC, and gas chromatography, LDI-Et was collected with a yield of 85% by mass with respect to the supplied reaction liquid (11-2).
  • reaction solution ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ / ( The molar amount of carbonyl compound) value was 2.2.
  • the liquid recovered in the storage tank 402 was 4.10 kg, and the recovery rate of LDI-Et was 120% by mass.
  • Step (12-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (15.8 mol) of 4,4′-methylenebis(cyclohexylamine) is transferred from the storage tank 101 through the line 11 to a baffled SUS. 2.29 kg (24.4 mol) of phenol was supplied from the storage tank 102 through the line 12 to the reaction vessel 104 and stirred to homogenize. Next, with the line 16 closed, 2.29 kg (24.4 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 11.27 kg (52.7 mol) of diphenyl carbonate was added. was supplied from the storage tank 103 to the reaction vessel 105 through the line 13 .
  • reaction solution (12-1) a carbamate compound corresponding to 4,4′-methylenebis(cyclohexylamine) was obtained in a yield of 99% by mass. had generated.
  • the line 16 was opened and the above reaction liquid (12-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (12-1) was 12.24 kg.
  • Step (12-2) Thermal Decomposition Step of Carbamate Compound Using 12.24 kg of reaction liquid (12-1) and 12.24 kg of diphenyl carbonate, reaction liquid (12-1) was added to the reactor over about 10 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.5, and a pressure of 11 to 16 kPa. A pyrolysis reaction was carried out in the same manner as in Example 1-1, except that the extraction of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 9.79 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (12-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-16).
  • Step (12-3) Low boiling point separation step
  • the reaction liquid (12-2) is continuously fed at 1.96 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.65 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1. 8.22 kg of the liquid recovered in the storage tank 303 was analyzed by NMR, LC, and gas chromatography. As a result, HMDI was recovered with a yield of 82% by mass with respect to the supplied reaction liquid (12-2).
  • Step (12-4) High boiling point separation step Example 1-1 except that the liquid recovered in the storage tank 303 in the step (12-3) was used, the operating temperature was 190 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 4.85 kg, and the recovery rate of HMDI was 125% by mass.
  • Step (13-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane is transferred from the storage tank 101 through the line 11 into a baffled SUS. Then, 4.11 kg (43.7 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12 and stirred to homogenize. Next, with the line 16 closed, 4.11 kg (43.7 mol) of phenol was supplied from the storage tank 102 through the line 15 to the baffled SUS reaction vessel 105, and 16.44 kg (76.8 mol) of diphenyl carbonate was added.
  • reaction solution (13-1) As a result of liquid chromatography analysis of the solution after the reaction (hereinafter also referred to as “reaction solution (13-1)”), a carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane was obtained at a yield of 99% by mass. had generated.
  • the line 16 was opened and the above reaction liquid (13-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (13-1) was 16.24 kg.
  • Step (13-3) Low boiling point separation step
  • the reaction liquid (13-2) is continuously fed at 2.79 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.90 kg/hour.
  • Low boiling point separation was performed in the same manner as in Example 1-1.
  • the liquid collected in the storage tank 303 was 9.50 kg, and as a result of analysis by NMR, LC, and gas chromatography, HXDI was collected with a yield of 77% by mass with respect to the supplied reaction liquid (13-2).
  • ⁇ 3 ⁇ (molar amount of isocyanurate group) + 2 ⁇ (molar amount of carbodiimide group) + 3 ⁇ (molar amount of uretonimine group) + 2 ⁇ (molar amount of allophanate group) ⁇ ⁇ (carbonyl compound (molar amount of) was 3.6.
  • Step (13-4) High boiling point separation step Example 1-1 except that the liquid recovered in the storage tank 303 in the step (13-3) was used, the operating temperature was 190 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid recovered in the storage tank 402 was 4.93 kg, and the recovery rate of HXDI was 122% by mass.
  • Step (1-1) Production Step of Carbamate Compound A reaction was carried out using the apparatus shown in FIG. The apparatus shown in FIG. 1 was also used in the production of carbamate compounds in Synthesis Example 1-1 and later. With the line 14 closed, 3.33 kg (19.2 mol) of 4-aminomethyl-1,8-octanediamine was supplied from the storage tank 101 through the line 11 to the baffled SUS reaction vessel 104.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 15.53 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (1-1) As a result of analyzing the solution after the reaction (hereinafter referred to as “reaction solution (1-1)”) by liquid chromatography, the yield of the carbamate compound corresponding to 4-aminomethyl-1,8-octanediamine was 99% by mass. was generated in The line 16 was opened, and the above reaction solution (1-1) was transferred to the storage tank 106 via the line 16 . The mass of the reaction liquid (1-1) was 19.40 kg.
  • Step (1-2): Thermal Decomposition Step of Carbamate Compound A reaction was carried out using the apparatus shown in FIG. The apparatus shown in FIG. 2 was also used for the thermal decomposition of the carbamate compounds in Synthesis Example 1-1 and later.
  • the line 24 closed 19.40 kg of diphenyl carbonate was supplied from the storage tank 202 through the line 22 to the baffled SUS reaction vessel 201 .
  • the temperature of the multistage distillation column 203 was raised to 170° C., the jacket temperature of the reaction vessel 201 was heated to 228° C., and the pressure was reduced to 14 kPa. 19.40 kg of the reaction liquid (1-1) collected in the storage tank 106 in the step (1-1) is heated to 120° C.
  • reaction solution (1-2) A part of this reaction solution (hereinafter referred to as “reaction solution (1-2)”) was purified with a column fractionator to isolate the carbonyl compound.
  • the isolated carbonyl compound is a mixture of compounds represented by the following formulas (I-1a) to (I-1c) (hereinafter, this mixture may be referred to as "mixture (I-1)"). Met.
  • TTI was produced with a yield of 70% by mass.
  • the apparatus shown in FIG. 3 was also used in the low boiling point separation in Synthesis Example 1-1 and later.
  • the reaction liquid (1-2) was continuously fed at 3.73 kg/hour from the storage tank 205 to the middle stage of the continuous multi-stage distillation column 301 through the line 31, and the liquid phase component was separated by distillation.
  • the amount of heat required for the distillation separation was supplied by circulating the liquid at the bottom of the column through reboiler A32 and line 33.
  • the liquid temperature at the bottom of the continuous multi-stage distillation column was 220°C, and the pressure at the top was 1.5 kPa.
  • reaction liquid (1-3) The liquid collected in the storage tank 303 (hereinafter referred to as "reaction liquid (1-3)") weighed 7.45 kg, and was analyzed by NMR, LC, and gas chromatography, and was found to be the supplied reaction liquid (1-2). TTI was recovered with a yield of 82% by weight.
  • the apparatus shown in FIG. 4 was also used in the high boiling point separation in Synthesis Example 1-1 and later.
  • a thin film distillation apparatus 401 manufactured by Kobelco Eco-Solutions Co., Ltd., Japan
  • the reaction liquid (1-3) recovered in the storage tank 303 in the step (1-3) is supplied to the upper part of the thin film distillation apparatus 401 at about 1.0 kg/hour through the line 41 to separate the isocyanate and the high-boiling components. gone.
  • the produced gaseous phase component was transferred to storage tank 402 via line 42 and condenser (condenser) A41.
  • the liquid recovered from the storage tank 402 was 3.35 kg, and the recovery rate of TTI was 121% by mass. The reason why the TTI recovery rate exceeds 100% by mass is that part of the isocyanate-modified product produced in the thermal decomposition step or the low boiling point separation step is regenerated into TTI.
  • Step (4-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (16.8 mol) of lysine ⁇ -aminoethyl ester trihydrochloride is transferred from the storage tank 101 through the line 11 to a baffled SUS Then, 2.52 kg (26.7 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12, and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 8.22 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (4-1) Liquid chromatography analysis of the solution after the reaction (hereinafter referred to as “reaction solution (4-1)”) revealed that a carbamate compound corresponding to lysine ⁇ -aminoethyl ester was produced at a yield of 96% by mass. .
  • Line 16 was opened, and the reaction solution (4-1) was transferred to storage tank 106 via line 16 .
  • the mass of the reaction liquid (4-1) was 11.45 kg.
  • Step (4-2) Thermal Decomposition Step of Carbamate Compound Using 11.45 kg of reaction solution (4-1) and 10.00 kg of diphenyl carbonate, reaction solution (4-1) was added to the reactor over about 15 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 3.2, and a pressure of 11 to 16 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 9.01 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (4-2)”) was purified with a column fractionator to isolate the carbonyl compound.
  • reaction solution (4-2) was purified with a column fractionator to isolate the carbonyl compound.
  • the isolated carbonyl compound was a mixture of compounds represented by the following formulas (I-4a) to (I-4c). (Hereinafter, this mixture may be referred to as "mixture (I-4)".) Further, as a result of analysis by NMR and gas chromatography, lysine triisocyanate (LTI) was produced with a yield of 77% by mass. rice field.
  • Step (4-3) Low boiling point separation step
  • the reaction liquid (4-2) is continuously fed at 1.80 kg/hour, and the withdrawal rate in the steady state of the line 34 is 1.10 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 5.50 kg, and as a result of analysis by NMR, LC, and gas chromatography, LTI was collected with a yield of 83% by mass with respect to the supplied reaction liquid (4-2).
  • the liquid collected in the storage tank 402 was 2.38 kg, and the recovery rate of LTI was 125% by mass.
  • Step (6-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (14.3 mol) of lysine methyl ester dihydrochloride is transferred from the storage tank 101 through the line 11 into the baffled SUS reaction vessel 104. , 1.91 kg (20.3 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12 and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, so that 5.93 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (6-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction solution (6-1)") by liquid chromatography, a carbamate compound corresponding to lysine methyl ester was produced with a yield of 97% by mass.
  • Line 16 was opened, and the reaction solution (6-1) was transferred to storage tank 106 via line 16 .
  • the mass of the reaction liquid (6-1) was 11.38 kg.
  • reaction solution (6-2) Thermal Decomposition Step of Carbamate Compound Using 11.38 kg of reaction liquid (6-1) and 11.38 kg of diphenyl carbonate, reaction liquid (6-1) was added to the reactor over about 12 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 0.9, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 19.35 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (6-2)”) was purified with a column fractionator to isolate the carbonyl compound.
  • the isolated carbonyl compound is a mixture of compounds represented by the following formulas (I-7a) to (I-7b) (hereinafter, this mixture may be referred to as "mixture (I-7)”) Met. Further, as a result of analysis by NMR and gas chromatography, lysine diisocyanate (LDI) was produced with a yield of 81% by mass.
  • the reaction liquid (6-2) is continuously fed at 3.87 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.47 kg/hour. Except for this, light boiling point separation was carried out in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 7.35 kg, and as a result of analysis by NMR, LC, and gas chromatography, LDI was collected with a yield of 86% by mass with respect to the supplied reaction liquid (6-2).
  • the liquid collected in the storage tank 402 was 4.57 kg, and the recovery rate of LDI was 122% by mass.
  • Step (9-1) Carbamate Compound Production Step Instead of 4-aminomethyl-1,8-octanediamine, 3.33 kg of hexamethylenediamine and 20.40 kg of diphenyl carbonate were used, and 5.50 kg of phenol was added.
  • the corresponding carbamate was synthesized from hexamethylenediamine in the same manner as in step (1-1), except that 5.50 kg of phenol was mixed with hexamethylenediamine and supplied to the reactor, and the reaction solution was heated to 120°C. Then, 15.42 kg of phenol in the liquid was extracted by setting the internal pressure to 1.0 kPa.
  • reaction liquid (9-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (9-1)") by liquid chromatography, a carbamate compound corresponding to hexamethylenediamine was produced with a yield of 99% by mass.
  • the mass of the reaction liquid (9-1) was 19.31 kg.
  • Step (9-2) Thermal Decomposition Step of Carbamate Compound Using 19.31 kg of reaction liquid (9-1) and 19.31 kg of diphenyl carbonate, reaction liquid (9-1) was added to the reactor over about 15 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 2.2, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. 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 the reaction solution (9-2) was isolated. The isolated carbonyl compound was a compound represented by the following formula (I-20).
  • HDI hexamethylene diisocyanate
  • Step (9-3) Low boiling point separation step
  • the reaction liquid (9-2) is continuously fed at 6.64 kg/hour, and the withdrawal rate in line 34 in a steady state is 0.930 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 4.65 kg, and as a result of analysis by NMR, LC, and gas chromatography, HDI was collected with a yield of 83% by mass with respect to the supplied reaction liquid (9-2).
  • Step (9-4) High boiling point separation step Synthesis Example 1-1 except that the liquid recovered in the storage tank 303 in the step (9-3) was used, the operating temperature was 170 ° C., and the internal pressure was 0.1 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 3.55 kg, and the recovery rate of HDI was 122% by mass.
  • Step (10-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (15.8 mol) of 4,4′-methylenebis(cyclohexylamine) is transferred from the storage tank 101 through the line 11 into a baffled SUS. 2.29 kg (24.4 mol) of phenol was supplied from the storage tank 102 through the line 12 to the reaction vessel 104 and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 6.94 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (10-1) a carbamate compound corresponding to 4,4′-methylenebis(cyclohexylamine) was obtained at a yield of 99% by mass. had generated.
  • the line 16 was opened and the above reaction liquid (10-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (8-1) was 12.24 kg.
  • Step (10-2) Thermal Decomposition Step of Carbamate Compound Using 12.24 kg of reaction liquid (10-1) and 12.24 kg of diphenyl carbonate, reaction liquid (10-1) was added to the reactor over about 10 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.5, and a pressure of 11 to 16 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 9.79 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (10-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-16).
  • HMDI methylenebis(cyclohexylisocyanate)
  • Step (10-3) Low boiling point separation step
  • the reaction liquid (10-2) is continuously fed at 1.96 kg/hour, and the withdrawal rate in the steady state of the line 34 is 1.65 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 8.22 kg, and as a result of analysis by NMR, LC, and gas chromatography, HMDI was collected with a yield of 82% by mass with respect to the supplied reaction liquid (10-2).
  • Step (10-4) High-boiling separation step Synthesis Example 1-1 except that the liquid recovered in the storage tank 303 in the step (10-3) was used, the operating temperature was 190 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid collected in the storage tank 402 was 4.85 kg, and the recovery rate of HMDI was 125% by mass.
  • Step (11-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (23.1 mol) of 1,3-di(aminomethyl)cyclohexane is transferred from the storage tank 101 through the line 11 into a baffled SUS. Then, 4.11 kg (43.7 mol) of phenol was supplied from the storage tank 102 to the reaction vessel 104 through the line 12 and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 11.74 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (11-1) As a result of analyzing the solution after the reaction (hereinafter also referred to as “reaction solution (11-1)”) by liquid chromatography, the yield of the carbamate compound corresponding to 1,3-di(aminomethyl)cyclohexane was 99% by mass. was generated in The line 16 was opened and the above reaction liquid (11-1) was transferred to the storage tank 106 via the line 16. The mass of the reaction liquid (11-1) was 16.24 kg.
  • reaction solution (11-2) Thermal Decomposition Step of Carbamate Compound Using 16.24 kg of reaction liquid (11-1) and 16.24 kg of diphenyl carbonate, reaction liquid (11-1) was added to the reactor over about 15 minutes. The reaction was started by supplying the reaction solution (11-1) at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.0, and a pressure of 11 to 16 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the extraction of phenol was continued. The mass of the reaction liquid transferred to the storage tank 205 was 13.97 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (11-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-19).
  • the reaction liquid (11-2) is continuously fed at 2.79 kg/hour, except that the withdrawal rate in the steady state of line 34 is 1.90 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 9.50 kg, and as a result of analysis by NMR, LC, and gas chromatography, HXDI was collected with a yield of 77% by mass with respect to the supplied reaction liquid (11-2).
  • the liquid collected in the storage tank 402 was 4.93 kg, and the recovery rate of HMDI was 122% by mass.
  • Step (12-1) Carbamate Compound Production Step Instead of 4-aminomethyl-1,8-octanediamine, 3.33 kg of 1,5-diaminopentane and 23.20 kg of diphenyl carbonate were used, and phenol 6 .48 kg of 1,5-diaminopentane was mixed with 1,5-diaminopentane, and 6.48 kg of phenol was fed to the reactor in the same manner as in step (1-1) of Synthesis Example 1-1 to obtain 1,5-diaminopentane. 18.01 kg of phenol in the liquid was extracted by heating the reaction liquid to 120° C. and adjusting the internal pressure to 1.0 kPa.
  • reaction solution (12-1) Liquid chromatography analysis of the solution after the reaction (hereinafter referred to as “reaction solution (12-1)”) revealed that a carbamate compound corresponding to 1,5-diaminopentane was produced at a yield of 99% by mass. .
  • the amount of 1,5-diaminopentane in the reaction liquid (12-1) was 21.48 kg.
  • Step (12-2) Thermal Decomposition Step of Carbamate Compound Using 21.48 kg of reaction liquid (12-1) and 21.48 kg of diphenyl carbonate, reaction liquid (12-1) was added to the reactor over about 11 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.5, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid after the reaction was 37.38 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (12-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-21).
  • Step (12-3) Low boiling point separation step
  • the reaction liquid (12-2) is continuously fed at 7.48 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.20 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 5.98 kg, and as a result of analysis by NMR, LC, and gas chromatography, PDI was collected with a yield of 87% by mass with respect to the supplied reaction liquid (12-2).
  • Step (12-4) High-boiling separation step Synthesis Example 1-1 except that the liquid recovered in the storage tank 303 in the step (12-3) was used, the operating temperature was 160 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid recovered in the storage tank 402 was 3.53 kg, and the recovery rate of PDI was 115%.
  • Step (13-1) Carbamate Compound Production Step 3.33 kg of isophoronediamine and 13.92 kg of diphenyl carbonate were used in place of 4-aminomethyl-1,8-octanediamine, and 3.22 kg of phenol was replaced with isophorone.
  • the corresponding carbamate was synthesized from isophoronediamine in the same manner as in step (1-1) of Synthesis Example 1-1, except that 3.22 kg of phenol was mixed with diamine and supplied to the reactor. 9.4 kg of phenol in the liquid was extracted by raising the temperature to °C and setting the internal pressure to 1.0 kPa.
  • reaction liquid (13-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (13-1)") by liquid chromatography, a carbamate compound corresponding to isophoronediamine was produced with a yield of 99% by mass.
  • the mass of the reaction liquid (13-1) was 14.29 kg.
  • reaction solution (13-2) Thermal Decomposition Step of Carbamate Compound Using 14.29 kg of reaction liquid (13-2) and 14.29 kg of diphenyl carbonate, reaction liquid (13-2) was added to the reactor over about 11 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.9, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid after the reaction was 23.44 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (13-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound is a mixture of compounds represented by the following formulas (I-22a) to (I-22b) (hereinafter, this mixture may be referred to as "mixture (I-22)”) Met.
  • IPDI isophorone diisocyanate
  • Step (13-3) Low boiling point separation step
  • the reaction liquid (13-2) is continuously fed at 4.69 kg/hour, and the withdrawal rate in line 34 in a steady state is 0.80 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 3.98 kg, and as a result of analysis by NMR, LC, and gas chromatography, IPDI was collected with a yield of 82% by mass with respect to the supplied reaction liquid (13-2).
  • the liquid collected in the storage tank 402 was 3.18 kg, and the recovery rate of IPDI was 120% by mass.
  • Step (14-1) Carbamate Compound Production Step Instead of 4-aminomethyl-1,8-octanediamine, 3.33 kg of xylylenediamine and 17.42 kg of diphenyl carbonate were used, and 4.45 kg of phenol was converted to xylylene. Synthesize the corresponding carbamate from xylylenediamine using the same method as in step (1-1) of Synthesis Example 1-1, except that 4.45 kg of phenol was mixed with diamine and supplied to the reactor, and the reaction solution was was heated to 120° C. and the internal pressure was set to 1.0 kPa to extract 12.64 kg of phenol in the liquid.
  • reaction liquid (14-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (14-1)") by liquid chromatography, a carbamate compound corresponding to xylylenediamine was produced with a yield of 98% by mass.
  • the mass of the reaction liquid (14-1) was 16.99 kg.
  • reaction solution (14-2) Thermal Decomposition Step of Carbamate Compound Using 16.99 kg of reaction liquid (14-1) and 16.99 kg of diphenyl carbonate, reaction liquid (14-1) was added to the reactor over about 11 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.5, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid after the reaction was 28.89 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (14-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-23).
  • xylylene diisocyanate (XDI) was produced with a yield of 78% by mass.
  • Step (14-3) Low boiling point separation step
  • the reaction liquid (14-2) is continuously fed at 5.78 kg/hour, and the withdrawal rate in line 34 in a steady state is 0.87 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 3.98 kg, and as a result of analysis by NMR, LC, and gas chromatography, XDI was collected with a yield of 88% by mass with respect to the supplied reaction liquid (14-2).
  • the liquid recovered in the storage tank 402 was 3.87 kg, and the recovery rate of XDI was 125% by mass.
  • Step (15-1) Carbamate Compound Production Step With the line 14 closed, 3.33 kg (16.8 mol) of 4,4′-diaminodiphenylmethane is transferred from the storage tank 101 through the line 11 into a baffled SUS reaction vessel. 104, 2.53 kg (27.0 mol) of phenol was supplied from the storage tank 102 through the line 12 to the reaction vessel 104 and stirred to homogenize.
  • the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to about 1 kPa, whereby 7.58 kg of phenol in the liquid was transferred to the storage tank 107 through the line 17 and the condenser (condenser) A11. pulled out.
  • reaction solution (15-1) Liquid chromatography analysis of the solution after the reaction (hereinafter referred to as “reaction solution (15-1)”) revealed that a carbamate compound corresponding to 4,4′-diaminodiphenylmethane was produced at a yield of 95% by mass. rice field.
  • the line 16 was opened and the above reaction liquid (15-1) was transferred to the storage tank 106 via the line 16.
  • the mass of the reaction liquid (15-1) was 12.77 kg.
  • reaction solution (15-2) Thermal Decomposition Step of Carbamate Compound Using 12.77 kg of reaction liquid (15-1) and 12.77 kg of diphenyl carbonate, reaction liquid (15-1) was added to the reactor over about 10 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 0.8, and a pressure of 11 to 16 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid transferred to the storage tank 205 was 11.75 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (15-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound was a compound represented by the following formula (I-13).
  • MDI was produced with a yield of 70% by mass.
  • Step (15-3) Low boiling point separation step
  • the reaction liquid (15-2) is continuously fed at 2.35 kg/hour, and the withdrawal rate in line 34 in a steady state is 1.97 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 9.87 kg, and as a result of analysis by NMR, LC, and gas chromatography, MDI was collected with a yield of 79% by mass with respect to the supplied reaction liquid (15-2).
  • the liquid collected in the storage tank 402 was 4.54 kg, and the recovery rate of MDI was 130% by mass.
  • Step (16-1) Carbamate Compound Production Step 3.33 kg of tolylene-2,4-diamine and 19.41 kg of diphenyl carbonate were used in place of 4-aminomethyl-1,8-octanediamine, and 5.15 kg of phenol. was mixed with xylylenediamine, and the corresponding carbamate was obtained from tolylene-2,4-diamine using the same method as in step (1-1) of Synthesis Example 1-1, except that 5.15 kg of phenol was fed to the reactor. was synthesized, the temperature of the reaction liquid was raised to 120° C., and the internal pressure was adjusted to 1.0 kPa to extract 14.49 kg of phenol in the liquid.
  • reaction liquid (16-1) As a result of analyzing the solution after the reaction (hereinafter referred to as "reaction liquid (16-1)") by liquid chromatography, the corresponding carbamate compound was produced with a yield of 96% by mass.
  • the mass of the reaction liquid (16-1) was 18.54 kg.
  • Step (16-2) Thermal Decomposition Step of Carbamate Compound Using 18.54 kg of reaction liquid (16-1) and 18.54 kg of diphenyl carbonate, reaction liquid (16-1) was added to the reactor over about 11 minutes. The reaction was started at a jacket temperature of 238° C., an internal temperature of 230° C., a reflux ratio of 4.7, and a pressure of 20 to 29 kPa. A thermal decomposition reaction was carried out in the same manner as in Synthesis Example 1-1, except that the withdrawal of was continued. The mass of the reaction liquid after the reaction was 11.75 kg. A part of this reaction solution (hereinafter referred to as “reaction solution (16-2)”) was purified with a column fractionator to isolate the carbonyl compound. The isolated carbonyl compound is a mixture of compounds represented by the following formulas (I-24a) to (I-24b) (hereinafter, this mixture may be referred to as "mixture (I-24)”) Met.
  • reaction solution (16-2) was purified with a column fractionator to isolate the carbon
  • Step (16-3) Low boiling point separation step
  • the reaction liquid (16-2) is continuously fed at 2.35 kg/hour, and the withdrawal rate in line 34 in a steady state is 0.94 kg/hour.
  • Low boiling point separation was performed in the same manner as in Synthesis Example 1-1.
  • the liquid collected in the storage tank 303 was 4.70 kg, and as a result of analysis by NMR, LC, and gas chromatography, TDI was collected with a yield of 85% by mass with respect to the supplied reaction liquid (16-2).
  • Step (16-4) High-boiling separation step Synthesis Example 1-1 except that the liquid recovered in the storage tank 303 in the step (16-3) was used, the operating temperature was 160 ° C., and the internal pressure was 0.3 kPa. High boiling point separation was carried out in the same manner as above.
  • the liquid recovered in the storage tank 402 was 3.27 kg, and the recovery rate of TDI was 119% by mass.
  • the carbamate compounds (III-1a) to (III-1c) are the mixture (III-1) thereof, the carbamate compounds (III-2a) to (III-2c) are the mixture (III-2) thereof, the carbamate compound (III -3a) to (III-3c) are mixtures thereof (III-3), carbamate compounds (III-4a) to (III-4c) are mixtures thereof (III-4), carbamate compounds (III-5a) to (III -5b) is a mixture thereof (III-5), carbamate compounds (III-7a) to (III-7b) are mixtures thereof (III-7), carbamate compounds (III-8a) to (III-8b) are mixtures thereof (III-8), carbamate compounds (III-10a) to (III-10b) are mixtures thereof (III-10), carbamate compounds (III-22a) to (III-22b) are mixtures thereof (III-11), Carbamate compounds (III-24a) to (III-24b) were obtained as their mixture (III-24).
  • the structures of these carbamate compounds are as described below.
  • Examples 1 to 62 and Comparative Examples 1 to 6 (Production of isocyanate compositions A-a1 to A-a46 and A-b1 to A-b6) Isocyanate compound (II), carbonyl compound (I), carbamate compound (III), and carbonate ester (IV) were mixed so that the types and contents were as shown in the following tables, and each isocyanate composition was prepared. Obtained.
  • the details of the types of isocyanate compound (II), carbonyl compound (I), carbamate compound (III), and carbonate ester (IV) used are as follows.
  • Carbonyl compound (I) As the carbonyl compound (I), compounds represented by the following formulas (I-1a) to (I-24b) obtained by the synthesis method described above were used. Incidentally, the carbonyl compounds (I-1a) to (I-1c) are the mixture (I-1) thereof, the carbonyl compounds (I-2a) to (I-2c) are the mixture (I-2) thereof, the carbonyl compounds (I-3a) to (I-3c) are mixtures thereof (I-3), carbonyl compounds (I-4a) to (I-4c) are mixtures thereof (I-4), carbonyl compounds (I-5a) to (I-5b) is a mixture thereof (I-5), carbonyl compounds (I-7a) to (I-7b) are mixtures thereof (I-7), carbonyl compounds (I-8a) to (I-8b) are The mixture (I-8), the carbonyl compounds (I-10a) to (I-10b) are the mixture (I-10), the carbonyl compounds (I-22a) to (I-22a)
  • carbamate compound (III) As the carbamate compound (III), compounds represented by the following formulas (III-1a) to (III-24b) obtained by the synthesis method described above were used.
  • the carbamate compounds (III-1a) to (III-1c) are the mixture (III-1) thereof, the carbamate compounds (III-2a) to (III-2c) are the mixture (III-2) thereof, the carbamate compound (III -3a) to (III-3c) are mixtures thereof (III-3), carbamate compounds (III-4a) to (III-4c) are mixtures thereof (III-4), carbamate compounds (III-5a) to (III -5b) is a mixture thereof (III-5), carbamate compounds (III-7a) to (III-7b) are mixtures thereof (III-7), carbamate compounds (III-8a) to (III-8b) are mixtures thereof (III-8), carbamate compounds (III-10a) to (III-10b) are mixtures thereof (III-10), carbamate compounds (III-22a) to (III-22b)
  • Carbonate ester (IV) As the carbonate ester (IV), the compounds shown below were used.
  • DPC diphenyl carbonate
  • GAC bis(2-methoxyphenyl) carbonate
  • DPCP bis(4-cumylphenyl) carbonate
  • the isocyanate compositions A-a1 to A-a62 (Examples 1 to 62) containing specific amounts of the isocyanate compound (II) and the carbonyl compound (I) are sufficiently suppressed in coloration, and Excellent storage stability. Further, in addition to isocyanate compound (II) and carbonyl compound (I), isocyanate compositions A-a1 to A-a8 and A-a11 to A-a18 further containing carbamate compound (III) and carbonate ester (IV) , and A-a21 to A-a62 (Examples 1 to 8, 11 to 18, and 21 to 62), the change in color difference before and after storage is smaller, the amount of denaturation is smaller, and the storage stability is particularly excellent.
  • the isocyanate composition A-b2 which does not contain the carbonyl compound (I) or has a content of the carbonyl compound (I) of more than 1.0 ⁇ 10 4 mass ppm relative to the total mass of the isocyanate composition
  • Ab5, and Ab6 Comparative Examples 2, 3, 5, and 6
  • a novel carbonyl compound can be provided.
  • the method for producing an isocyanate compound of the present embodiment is a method using the carbonyl compound, and can prevent by-products from sticking to equipment during the production of the isocyanate compound and improve the yield of the isocyanate compound.
  • the isocyanate composition of the present embodiment it is possible to provide an isocyanate composition in which coloration is sufficiently suppressed and which has excellent storage stability.

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