Method for producing polyamine compound

Abstract

This method for producing a polyamine compound comprises: a preparation step for preparing an isocyanurate composition containing an isocyanurate compound; and a reaction step for obtaining a polyamine compound by reacting the isocyanurate compound with a compound represented by general formula. (In the general formula, n is 1 or 2. R1 represents an amino group or a hydroxyl group. R2 represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and may be substituted by an amino group or a hydroxyl group. > # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a method for producing a polyamine compound. Background Art

[0002] Conventionally, polyamine compounds are known as raw materials for polyisocyanate compounds.

[0003] For example, xylylenediamine hydrochloride is reacted with phosgene to produce xylylenediisocyanate (see Patent Document 1 below).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: International Publication No. 2018 / 190290 Summary of the Invention

[0007] Problems to be solved by the invention

[0008] There is a strong desire to efficiently produce a polyamine compound that can be used in the production of a polyisocyanate compound such as that described in Patent Document 1.

[0009] The present invention provides a method for producing a polyamine compound, which can produce the polyamine compound efficiently.

[0010] Means for solving problems

[0011] The present invention [1] includes a method for producing a polyamine compound, comprising the following steps: a preparation step of preparing an isocyanurate composition containing an isocyanurate compound; and a reaction step of reacting the isocyanurate compound with a compound represented by the following general formula to obtain a polyamine compound.

[0012] general formula:

[0013] [Chemical Formula 1]

[0014]

[0015] (In the above general formula, n is 1 or 2. R1 represents an amino group or a hydroxyl group. R2 is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, and may be substituted with an amino group or a hydroxyl group.)

[0016] The present invention [2] includes the method for producing a polyamine compound according to the above-mentioned [1], wherein the isocyanurate composition further contains a polyisocyanate compound.

[0017] The present invention [3] includes the method for producing a polyamine compound according to the above-mentioned [2], wherein the polyisocyanate compound is produced by a production method comprising the following steps: an isocyanation step of reacting the polyamine compound with phosgene to obtain a reaction product containing the polyisocyanate compound; and a detarring step of removing a tar component from the reaction product, wherein the isocyanurate composition is the tar component removed by the detarring step.

[0018] The present invention [4] includes the method for producing a polyamine compound according to [2] or [3], wherein the polyisocyanate compound is at least one selected from the group consisting of xylylenediisocyanate, bis(isocyanatemethyl)bicyclo[2,2,1]heptane, and bis(isocyanatemethyl)cyclohexane.

[0019] The present invention [5] includes the method for producing a polyamine compound according to the above [4], wherein the polyisocyanate compound is xylylenediisocyanate.

[0020] Effects of the Invention

[0021] According to the method for producing a polyamine compound of the present invention, in the reaction step, an isocyanurate compound is reacted with the specific compound represented by the above general formula.

[0022] Thereby, the isocyanurate compound can be efficiently decomposed to obtain the polyamine compound.

[0023] As a result, the polyamine compound can be produced efficiently. DETAILED DESCRIPTION

[0024] In the method for producing a polyamine compound of the present invention, for example, a tar component generated in the production of a polyisocyanate composition is used as a raw material, and the isocyanurate compound in the tar component is decomposed to produce the polyamine compound.

[0025] First, the production of the polyisocyanate composition will be described.

[0026] 1. Method for producing polyisocyanate composition

[0027] The polyisocyanate composition contains a polyisocyanate compound as a main component.

[0028] Examples of the polyisocyanate compound include industrially common polyisocyanates, and examples of the polyisocyanate include chain aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

[0029] Examples of the chain aliphatic polyisocyanate include pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI).

[0030] Examples of the alicyclic polyisocyanate include isophorone diisocyanate (IPDI), bis(isocyanatemethyl)bicyclo[2,2,1]heptane (BIBH), hydrogenated diphenylmethane diisocyanate (H 12 MDI), and bis(isocyanatemethyl)cyclohexane (BIC).

[0031] Examples of the aromatic polyisocyanate include toluene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).

[0032] Examples of the aromatic aliphatic polyisocyanate include xylylenediisocyanate (XDI) and tetramethylxylylenediisocyanate (TMXDI).

[0033] Examples of the polyisocyanate compound include preferably chain aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic aliphatic polyisocyanates, and more preferably include xylylenediisocyanate (XDI), isophorone diisocyanate (IPDI), bis(isocyanatemethyl)bicyclo[2,2,1]heptane (BIBH), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), bis(isocyanatemethyl)cyclohexane (BIC), and hydrogenated diphenylmethane diisocyanate (HDI). 12 MDI), more preferably xylylenediisocyanate (XDI), bis(isocyanatemethyl)bicyclo[2,2,1]heptane (BIBH), and bis(isocyanatemethyl)cyclohexane (BIC). Xylylenediisocyanate has two structural isomers, 1,3-xylylenediisocyanate and 1,4-xylylenediisocyanate. Preferably, xylylenediisocyanate is 1,3-xylylenediisocyanate. Bis(isocyanatemethyl)cyclohexane has two structural isomers, 1,3-bis(isocyanatemethyl)cyclohexane and 1,4-bis(isocyanatemethyl)cyclohexane. Preferably, bis(isocyanatemethyl)cyclohexane is 1,3-bis(isocyanatemethyl)cyclohexane (1,3-BIC).

[0034] The content of the polyisocyanate compound in the polyisocyanate composition is, for example, 98.00% by mass or more, preferably 99.00% by mass or more, more preferably 99.30% by mass or more, and even more preferably 99.60% by mass or more, for example, 99.95% by mass or less. The polyisocyanate composition preferably contains only the polyisocyanate compound.

[0035] When the polyisocyanate compound is xylylenediisocyanate, the content ratio of xylylenediisocyanate in the polyisocyanate composition can be measured by the method described in paragraphs

[0376] and

[0377] of International Publication No. 2018 / 190290.

[0036] The method for producing a polyisocyanate composition includes a salt-making step, an isocyanate-forming step, a degassing step, a desolvation step, a detarring step, and a purification step. The method for producing a polyisocyanate composition sequentially carries out the salt-making step, the isocyanate-forming step, the degassing step, the desolvation step, the detarring step, and the purification step.

[0037] (1) Salt production process

[0038] In the salt-making process, for example, a polyamine compound and hydrogen chloride are mixed in the presence of an inert solvent. Specifically, in the salt-making process, hydrogen chloride gas is first introduced into the inert solvent. Next, a polyamine solution, obtained by dissolving the polyamine compound in the inert solvent, is supplied to the inert solvent into which the hydrogen chloride gas has been introduced. The inert solvent, the polyamine compound, and hydrogen chloride are then mixed. This produces a slurry containing the hydrochloride salt of the polyamine compound.

[0039] Examples of the polyamine compound include polyamines corresponding to the above-mentioned polyisocyanate compounds, and examples of the polyamine compound include chain aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and aromatic aliphatic polyamines.

[0040] Examples of the chain aliphatic polyamine include pentamethylenediamine and hexamethylenediamine.

[0041] Examples of the alicyclic polyamine include isophoronediamine, bis(aminomethyl)bicyclo[2,2,1]heptane, hydrogenated diphenylmethanediamine, and bis(aminomethyl)cyclohexane (BAC).

[0042] Examples of the aromatic polyamine include toluenediamine and diphenylmethanediamine.

[0043] Examples of the aromatic aliphatic polyamine include xylylenediamine and tetramethylxylylenediamine.

[0044] When the polyisocyanate compound is 1,3-xylylenediisocyanate, the polyamine compound is 1,3-xylylenediamine. When the polyisocyanate compound is bis(isocyanatemethyl)bicyclo[2,2,1]heptane, the polyamine compound is bis(aminomethyl)bicyclo[2,2,1]heptane. When the polyisocyanate compound is 1,3-bis(isocyanatemethyl)cyclohexane, the polyamine compound is 1,3-bis(aminomethyl)cyclohexane (1,3-BAC).

[0045] Examples of the inert solvent include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing compounds, ethers, ketones, fatty acid esters, and aromatic carboxylic acid esters.

[0046] Examples of the aromatic hydrocarbons include benzene, toluene, and xylene.

[0047] Examples of the aliphatic hydrocarbon include octane and decane.

[0048] Examples of the alicyclic hydrocarbon include cyclohexane, methylcyclohexane, and ethylcyclohexane.

[0049] Examples of the halogenated aromatic hydrocarbon include chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene.

[0050] Examples of the nitrogen-containing compound include nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N′-dimethylimidazolidinone.

[0051] Examples of the ether include dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

[0052] Examples of the ketone include heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl ketone.

[0053] Examples of the fatty acid ester include ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate.

[0054] Examples of the aromatic carboxylic acid ester include methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate.

[0055] The inert solvents can be used alone or in combination of two or more.

[0056] As the inert solvent, preferably, halogenated aromatic hydrocarbons are used, and more preferably, chlorobenzene and dichlorobenzene are used.

[0057] The content of the polyamine compound in the amine solution is not limited. The content of the polyamine compound in the amine solution is, for example, 3.0 mass % or more, preferably 5.0 mass % or more, for example, 30 mass % or less, preferably 20 mass % or less.

[0058] The ratio of the mass of the supplied polyamine compound to the total mass of the polyamine compound and the inert solvent (total amine concentration) is, for example, 3 mass % or more, preferably 5 mass % or more, for example, 30 mass % or less, preferably 20 mass % or less, more preferably 15 mass % or less.

[0059] The supply ratio of hydrogen chloride relative to 1 mol of the polyamine compound is, for example, 2 mol or more, for example, 10 mol or less, preferably 6 mol or less, and more preferably 4 mol or less.

[0060] The temperature of the salt-making step is, for example, 30°C or higher, preferably 50°C or higher, more preferably 60°C or higher, and for example, 160°C or lower, preferably 150°C or lower, more preferably 140°C or lower.

[0061] The pressure (gauge pressure) in the salt production process is, for example, atmospheric pressure (0 MPaG) or higher, preferably 0.01 MPaG or higher, more preferably 0.02 MPaG or higher, and for example, 1.0 MPaG or lower, preferably 0.5 MPaG or lower, more preferably 0.4 MPaG or lower.

[0062] (2) Isocyanate process

[0063] In the isocyanate formation step, the hydrochloride of the polyamine compound is reacted with phosgene (hydrochloride method). Specifically, in the isocyanate formation step, phosgene is added to the slurry obtained in the salt-making step to react the hydrochloride of the polyamine compound with phosgene. This produces a reaction product containing a polyisocyanate compound.

[0064] The supply ratio of phosgene to 1 mol of the hydrochloride of the polyamine compound is, for example, 4 mol or more, preferably 5 mol or more, more preferably 6 mol or more, and for example, 50 mol or less, preferably 40 mol or less, more preferably 30 mol or less.

[0065] The time for the isocyanate formation step is, for example, 4 hours or more, preferably 6 hours or more, and for example, 25 hours or less, preferably 20 hours or less, and more preferably 15 hours or less.

[0066] The temperature of the isocyanate formation step is, for example, 90° C. or higher, preferably 100° C. or higher, more preferably 110° C. or higher, and is, for example, 190° C. or lower, preferably 180° C. or lower, more preferably 160° C. or lower.

[0067] The pressure (gauge pressure) in the isocyanate formation step is, for example, greater than atmospheric pressure (0 MPaG), preferably 0.0005 MPaG or higher, more preferably 0.001 MPaG or higher, further preferably 0.003 MPaG or higher, particularly preferably 0.01 MPaG (10 kPaG) or higher, particularly preferably 0.02 MPaG (20 kPaG) or higher, most preferably 0.03 MPaG (30 kPaG) or higher, and is, for example, 0.6 MPaG or lower, preferably 0.4 MPaG or lower, and more preferably 0.2 MPaG or lower.

[0068] The isocyanate formation step is preferably carried out in a continuous manner. That is, in the isocyanate formation step, the slurry obtained in the salt formation step is continuously transferred from the container used in the salt formation step to the reaction container used in the isocyanate formation step, and the hydrochloride of the polyamine compound and phosgene are reacted in the reaction container while the resulting reaction product (reaction material) is continuously removed from the reaction container.

[0069] In the isocyanate formation step, carbamoyl chloride is generated by the reaction of the polyamine compound and phosgene, and the polyisocyanate compound is generated by the decomposition reaction of the carbamoyl chloride.

[0070] Here, in the isocyanate formation step, the generated polyisocyanate compound reacts with carbamoyl chloride as an intermediate, thereby generating an isocyanurate compound as a by-reaction.

[0071] Taking the case where the polyamine compound is xylylenediamine as an example, as shown in the following reaction formula (1), two molecules of xylylenediisocyanate react with one molecule of carbamoyl chloride, thereby generating one molecule of an isocyanurate compound and one molecule of chloromethylbenzyl isocyanate as side reactions.

[0072] Reaction (1)

[0073] [Chemical Formula 1]

[0074]

[0075] (3) Degassing process

[0076] In the degassing step, a known degassing tower is used to remove excess phosgene and gases such as hydrogen chloride generated as a by-product of the reaction from the reaction product.

[0077] (4) Desolventization process

[0078] In the desolventizing step, the inert solvent is distilled off from the reaction product using a known distillation column.

[0079] (5) Detarring process

[0080] In the detarring step, the tar component is removed from the reaction product using a known detarrifier.

[0081] The tar component contains the isocyanurate compound in the above reaction formula (1).

[0082] The content of the isocyanurate compound in the tar component is, for example, 50 mass % or more, preferably 70 mass % or more, and for example, 90 mass % or less, preferably 80 mass % or less.

[0083] In the detarring step, a portion of the polyisocyanate compound in the reaction product is removed from the reaction product as a tar component together with the isocyanurate compound. Therefore, the tar component contains the polyisocyanate compound.

[0084] The content of the polyisocyanate compound in the tar component is, for example, 10 mass % or more, preferably 20 mass % or more, and for example, 50 mass % or less, preferably 30 mass % or less.

[0085] (6) Purification process

[0086] In the purification step, the reaction product after the detarring step is purified to adjust the content of the polyisocyanate compound to fall within the above-mentioned range.

[0087] Examples of purification methods include crystallization and distillation, with distillation being preferred. To purify the reaction product by distillation, for example, low-boiling substances (low-boiling point components) are removed from the reaction product by distillation, and then the reaction product after the removal of the low-boiling substances is subjected to rectification. Specifically, the purification process includes a low-boiling point removal step of distilling the low-boiling substances from the reaction product, and a rectification step of rectifying the reaction product after the removal of the low-boiling substances.

[0088] 2. Method for producing polyamine compounds

[0089] Next, the method for producing the polyamine compound will be described.

[0090] The method for producing a polyamine compound includes a preparation step and a reaction step.

[0091] (1) Preparation process

[0092] In the preparation step, an isocyanurate composition is prepared. In this embodiment, the isocyanurate composition is the tar component removed in the detarring step during the production of the polyisocyanate composition. Therefore, the isocyanurate composition contains the isocyanurate compound in the above reaction formula (1) and the polyisocyanate compound.

[0093] (2) Reaction process

[0094] In the reaction step, the compound represented by the following general formula is mixed with the isocyanurate composition and heated, thereby reacting the isocyanurate compound and the polyisocyanate compound with the compound represented by the following general formula.

[0095] general formula:

[0096] [Chemical Formula 2]

[0097]

[0098] In the above general formula, n is 1 or 2. In the above general formula, R1 represents an amino group or a hydroxyl group.

[0099] In the above general formula, R2 is a linear or branched hydrocarbon group having 1 to 10 carbon atoms.

[0100] Examples of the linear or branched hydrocarbon group having 1 to 10 carbon atoms include linear or branched aliphatic hydrocarbon groups having 1 to 10 carbon atoms and aromatic hydrocarbon groups having 6 to 10 carbon atoms.

[0101] Examples of the linear or branched aliphatic hydrocarbon group having 1 to 10 carbon atoms include linear alkyl groups having 1 to 10 carbon atoms and branched alkyl groups having 3 to 10 carbon atoms.

[0102] Examples of the linear alkyl group having 1 to 10 carbon atoms include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, and n-decyl.

[0103] Examples of the branched alkyl group having 3 to 12 carbon atoms include isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl.

[0104] Examples of the aromatic hydrocarbon group having 6 to 10 carbon atoms include a phenyl group and a naphthyl group.

[0105] R2 may be substituted with an amino group or a hydroxy group.

[0106] As the compound represented by the above general formula, when n is 1, specific examples include diethylenetriamine, N-methylethylenediamine, N-phenylethylenediamine, and diethanolamine. In addition, as the compound represented by the above general formula, when n is 2, specific examples include dipropylenetriamine and dipropanolamine. As the compound represented by the following general formula, preferably diethylenetriamine and dipropylenetriamine are mentioned.

[0107] The compound represented by the above general formula has a boiling point at 1 atm of, for example, 110°C or higher, preferably 120°C or higher, more preferably 140°C or higher, more preferably 160°C or higher, more preferably 180°C or higher, more preferably 200°C or higher, for example 300°C or lower.

[0108] The compound represented by the above general formula is mixed in an amount of, for example, 2 mol or more, preferably 4 mol or more, more preferably 6 mol or more, for example 30 mol or less, preferably 20 mol or less, more preferably 10 mol or less, per 1 mol of the isocyanurate compound.

[0109] The heating temperature in the reaction step is, at normal pressure, for example, 100°C or higher, preferably 120°C or higher, more preferably 150°C or higher, and for example, 300°C or lower, preferably 250°C or lower.

[0110] The heating time in the reaction step is, for example, 1 hour or longer, preferably 3 hours or longer, and for example, 10 hours or shorter, preferably 8 hours or shorter.

[0111] During the reaction process, the isocyanurate compound is decomposed by the compound represented by the above general formula, thereby producing a polyamine compound. When n in the above general formula is 1 and R1 is an amino group, an imidazolidinone is produced as a side reaction during the reaction process. It should be noted that when n in the above general formula is 1 and R1 is a hydroxyl group, an oxazolidinone is produced as a side reaction instead of the imidazolidinone. Furthermore, when n in the above general formula is 2 and R1 is an amino group, a tetrahydropyrimidone is produced as a side reaction instead of the imidazolidinone during the reaction process. Furthermore, when n in the above general formula is 2 and R1 is a hydroxyl group, an oxazinone is produced as a side reaction instead of the imidazolidinone during the reaction process.

[0112] Taking the case where the isocyanurate composition is a tar component generated in the production of xylylenediisocyanate and the compound represented by the above general formula is diethylenetriamine as an example, as shown in the following reaction formula (2), the isocyanurate compound reacts with diethylenetriamine to produce xylylenediamine and imidazolidinone (specifically, 3-aminoethyl-2-imidazolidinone). Furthermore, as shown in the following reaction formula (3), the xylylenediisocyanate in the tar component reacts with diethylenetriamine to produce xylylenediamine and imidazolidinone.

[0113] Reaction formula (2):

[0114] [Chemical Formula 3]

[0115]

[0116] Reaction formula (3):

[0117] [Chemical Formula 4]

[0118]

[0119] When the isocyanurate composition is a tar component generated during the production of xylylenediisocyanate and the compound represented by the general formula is dipropylenetriamine, the isocyanurate compound reacts with dipropylenetriamine as shown in the following reaction formula (4) to produce xylylenediamine and tetrahydropyrimidone (specifically, 1-(3-aminopropyl)tetrahydropyrimidin-2(1H)-one). Furthermore, as shown in the following reaction formula (5), the xylylenediisocyanate in the tar component reacts with dipropylenetriamine to produce xylylenediamine and tetrahydropyrimidone.

[0120] Reaction formula (4):

[0121] [Chemical Formula 5]

[0122]

[0123] Reaction formula (5):

[0124] [Chemical Formula 6]

[0125]

[0126] By decomposing the isocyanurate compound using the compound represented by the above general formula, the isocyanurate compound can be decomposed by a simple step of heating at normal pressure, and the polyamine compound can be produced efficiently.

[0127] Then, the imidazolidinone may be decomposed by adding, for example, sodium hydroxide to the reaction solution obtained in the reaction step and heating the mixture. Diethylenetriamine is produced by the decomposition of the imidazolidinone.

[0128] Furthermore, the reaction liquid obtained in the reaction step is subjected to distillation and rectification to obtain a xylylenediamine composition containing xylylenediamine.

[0129] The content of xylylenediamine in the xylylenediamine composition is, for example, 98.00 mass % or more, preferably 99.00 mass % or more, more preferably 99.30 mass % or more, further preferably 99.60 mass % or more, and for example, 99.95 mass % or less, preferably 99.90 mass % or less.

[0130] The obtained xylylenediamine composition can be used for the production of xylylenediisocyanate. The obtained xylylenediamine composition may contain diethylenetriamine to such an extent that it can be used for the production of xylylenediisocyanate.

[0131] 3. Effects

[0132] According to the method for producing a polyamine compound, an isocyanurate compound and the specific compound represented by the above general formula are reacted in the reaction step.

[0133] Thereby, the isocyanurate compound can be efficiently decomposed to obtain the polyamine compound.

[0134] As a result, the polyamine compound can be produced efficiently.

[0135] Furthermore, if a tar component generated in the production of a polyisocyanate composition is used as the isocyanurate composition as a raw material, the raw material cost consumed in the production of the polyamine compound can be reduced.

[0136] Furthermore, if a polyamine compound produced from a tar component is used for the production of a polyisocyanate composition, the raw material cost consumed in the production of the polyisocyanate composition can also be reduced.

[0137] Furthermore, if a tar component is used as the isocyanurate composition, the amount of tar components discarded during the production of the polyisocyanate composition can be reduced, thereby reducing the environmental load caused by the disposal of the tar components.

[0138] Furthermore, when a tar component is used as the isocyanurate composition, a polyamine compound can also be produced from the polyisocyanate compound in the tar component.

[0139] Therefore, it is possible to suppress the polyisocyanate compound from being discarded as a tar component.

[0140] 4. Modifications

[0141] The isocyanate formation method in the production of the polyisocyanate composition is not limited to the hydrochloride method described above, and the isocyanate formation step can also be performed by a hot and cold two-step method or a phosgene pressure method.

[0142] When the isocyanate formation step is carried out using the hot / cold two-step method, first, the polyamine compound is dissolved in the aforementioned inert solvent to obtain a polyamine solution. Next, phosgene in an amount of about 5 to 20 times the molar amount of the polyamine compound is introduced into the polyamine solution, and the polyamine compound and phosgene are reacted at, for example, 0 to 90°C (reaction in the first step). Next, the polyamine compound and phosgene are reacted in the presence of about 0.5 to 10 times the molar amount of phosgene relative to the polyamine compound, for example, at 100 to 150°C (reaction in the second step).

[0143] When the isocyanate formation step is carried out by the phosgene pressure method, the polyamine compound is heated to a temperature above the boiling point of the polyamine compound, and then, for example, 1 to 10 times the mole of phosgene as much as the polyamine compound is introduced together with a carrier gas such as nitrogen or argon under a pressure of 100 to 500 kPa to react the polyamine compound with the phosgene.

[0144] When the isocyanate formation step is carried out by a hot-cold two-step method or a phosgene pressure method, a tar component containing an isocyanurate compound is also generated.

[0145] The isocyanurate composition may be a tar component generated during the production of a polyisocyanate composition using a hot-cold two-step method or a phosgene pressure method.

[0146] The isocyanurate composition is not limited to the tar component generated during the production of the polyisocyanate composition. For example, the isocyanurate composition may be a distillation residue generated during the purification step of the polyisocyanate composition. Specifically, the isocyanurate composition may be a distillation residue generated during the rectification of the reaction product after distillation to remove low-boiling-point substances during the aforementioned purification step. Furthermore, the isocyanurate composition may be a mixture of the tar component and the distillation residue generated during the purification step.

[0147] In addition, the isocyanurate compound in the isocyanurate composition is not limited to the isocyanurate of xylylenediisocyanate. Examples of the isocyanurate compound in the isocyanurate composition include pentamethylene diisocyanate (PDI), hexamethylene diisocyanate (HDI), bis(isocyanatemethyl)bicyclo[2,2,1]heptane (BIBH), isophorone diisocyanate (IPDI), bis(isocyanatemethyl)cyclohexane (BIC), and hydrogenated diphenylmethane diisocyanate (HDI). 12 MDI).

[0148] Example

[0149] The following examples illustrate the present invention in more detail, but the present invention is not limited thereto. The specific numerical values ​​of the mixing ratios (content ratios), physical property values, parameters, etc. used in the following descriptions may be replaced by the corresponding upper limits (values ​​defined as "below" or "less than") or lower limits (values ​​defined as "above" or "greater than") of the mixing ratios (content ratios), physical property values, parameters, etc. described in the "Specific Embodiments" above. It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0150] 1. Production of polyisocyanate composition

[0151] (1) Production Example 1 (Production of XDI Composition)

[0152] An XDI composition was produced under the conditions of Example 2 of International Publication No. 2018 / 190290. It should be noted that in the step of detarring the desolventized material to prepare the detarred material (detarring step), specifically, the tar component is removed from the desolventized material (detarring) to prepare the detarred material.

[0153] (2) Production Example 2 (Production of BIBH Composition)

[0154] An autoclave (with an internal volume of 2 m3) equipped with a reflux condenser, a stirring blade, a thermometer, a hydrogen chloride gas inlet pipe, a phosgene inlet pipe, a raw material tank, a raw material feed pump, and a pressure regulator was used. 3 ) as a reactor.

[0155] 958 g of o-dichlorobenzene as a reaction solvent was added to the reactor, and 154.2 g (1.0 mol) of a mixture of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane (polyamine compound) and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane (polyamine compound) and 702 g of o-dichlorobenzene (inert solvent) (total amine concentration: 8.5 mass %) were added to the raw material tank.

[0156] Next, after the temperature inside the reactor was raised to 120°C, the pressure inside the autoclave was adjusted to 0.01 MPa above atmospheric pressure. Hydrogen chloride gas was then introduced into the reactor through the hydrogen chloride gas inlet pipe at a rate of 43.8 g / hr. Simultaneously, a mixture of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane diluted with a solvent was introduced from the raw material tank using a raw material feed pump at a rate of 428.1 g / hr. The entire amount was introduced over two hours. Furthermore, the mixture was aged for one hour while adding hydrogen chloride gas at a rate of 20 g / hr. This yielded a hydrochloride slurry containing the hydrochloride salts of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane (salting step).

[0157] Next, the hydrochloride slurry was heated to 160°C in the reactor, and phosgene was blown in at 100 g / hr (1.0 mol / hr) from the phosgene inlet tube. The reaction was continued for 8 hours while maintaining the temperature. This yielded a reaction product containing 2,5-bis(isocyanatemethyl)bicyclo[2.2.1]heptane (polyisocyanate compound) and 2,6-bis(isocyanatemethyl)bicyclo[2.2.1]heptane (polyisocyanate compound) (isocyanation step).

[0158] After the reaction was completed, the system was purged with nitrogen to remove unreacted phosgene and hydrogen chloride gas (degassing step). The reaction solution was then filtered to remove 0.5 g (dry weight) of unreacted hydrochloride.

[0159] From the obtained filtrate, o-dichlorobenzene was removed (desolventizing step), and tar components were removed (detarring step), thereby obtaining 206.9 g of a BIBH composition having a BIBH purity of 98.5% by mass.

[0160] Next, the obtained BIBH composition was subjected to fractionation to obtain a BIBH composition having a BIBH purity of 99.99% by mass (purification step).

[0161] (3) Production Example 3 (Production of 1,3-BIC Composition)

[0162] The salt formation step, isocyanate formation step, degassing step, desolvation step, detarring step, and purification step were carried out in the same manner as in Production Example 2, except that the mixture of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane was replaced with 1,3-bis(aminomethyl)cyclohexane (polyamine compound). Thus, a 1,3-BIC composition containing 1,3-bis(isocyanatemethyl)cyclohexane (polyisocyanate compound) was obtained.

[0163] 2. Production of polyamine compounds

[0164] (1) Example 1

[0165] The tar component (isocyanurate composition, hereinafter referred to as XDI tar) removed from the desolvated material in the detarring step of Production Example 1 was prepared (preparation step).

[0166] Tar components were analyzed by infrared spectroscopy. The results showed that, similar to cyanuric acid, 1690 cm -1 Therefore, it is estimated that the tar component contains a compound containing an isocyanurate skeleton.

[0167] Next, 50.00 parts by mass of XDI tar was placed in the reactor, and then 144.73 parts by mass of diethylenetriamine was added dropwise to the reactor at room temperature over 10 minutes to mix the XDI tar and diethylenetriamine.

[0168] Next, the XDI tar and diethylenetriamine in the reactor were heated to an internal temperature of 185° C. under normal pressure and reacted with stirring for 6 hours to obtain a polyamine composition containing xylylenediamine (polyamine compound) (reaction step).

[0169] During the reaction step, the concentration of xylylenediamine in the mixture of XDI tar and diethylenetriamine was measured by gas chromatography at regular intervals. The reaction step was terminated when the concentration of xylylenediamine stopped changing. The measurement conditions for gas chromatography are shown below.

[0170] <Gas Chromatography Measurement Conditions>

[0171] Installation: SHIMADZU GC-2014

[0172] Column: DB-1 (membrane thickness 1.5 μm, inner diameter 0.53 mm × length 60 m, manufactured by Agilent)

[0173] Column oven temperature: maintain at 50°C for 2 minutes, increase the temperature from 50°C to 150°C at 10°C / min, maintain for 5 minutes after reaching 150°C, increase the temperature from 150°C to 300°C at 10°C / min, maintain for 10 minutes after reaching 300°C.

[0174] Injection method: Pulse splitless method

[0175] Inlet temperature: 250℃

[0176] Detector temperature: 300°C

[0177] Carrier gas: N2 158kPa, H2 55kPa, air 45kPa (constant pressure control)

[0178] Internal standard substance: 2,2,6,6,-tetramethylpiperidine 50 mg

[0179] Solvent: A mixture of dichloromethane and methanol in a ratio of 1:1

[0180] Sample concentration: 50 mg / 5 mL

[0181] Injection volume: 1 μL

[0182] Detection method: FID

[0183] The molar number of xylylenediamine obtained from the gas chromatography results was converted into mass to calculate the yield of xylylenediamine. The retention time of xylylenediamine was 25.2 minutes.

[0184] At the time of completion of the reaction step, the yield of xylylenediamine was 50.02%. The yield was calculated using the following formula.

[0185] Yield = mass of generated polyamine compound / mass of tar component × 100

[0186] Next, the obtained polyamine composition was cooled to an internal temperature of 145° C., and 44.81 parts by mass of granular sodium hydroxide was added to the cooled polyamine composition, followed by stirring for 3 hours to decompose the imidazolidinone in the polyamine composition.

[0187] Next, the polyamine composition was filtered under reduced pressure, and the filter residue was washed twice with 30.00 parts by mass of methanol.

[0188] Next, methanol was distilled off from the filtrate using an evaporator. The concentration of xylylenediamine in the filtrate after distillation of methanol was measured by gas chromatography, and the yield was calculated using the above formula. The yield of xylylenediamine was 44.62%.

[0189] Next, the filtrate after distilling off the methanol was subjected to reduced pressure distillation to obtain a mixture of xylylenediamine and diethylenetriamine as a fraction.

[0190] The concentration of xylylenediamine in the fraction was measured by gas chromatography, and the yield was calculated using the above formula. As a result, the yield of xylylenediamine was 37.84%.

[0191] (2) Example 2

[0192] The tar component (isocyanurate composition, hereinafter referred to as BIBH tar) obtained in the detarring step of Production Example 2 was prepared (preparation step).

[0193] The tar components were analyzed by infrared spectroscopy. The results showed that the 1690 cm -1 Therefore, it is estimated that the tar component contains a compound containing an isocyanurate skeleton.

[0194] Next, 20.00 parts by mass of BIBH tar was placed in the reactor, and then 73.81 parts by mass of diethylenetriamine was added dropwise to the reactor at room temperature over 10 minutes to mix the XDI tar and diethylenetriamine.

[0195] Next, the BIBH tar and diethylenetriamine in the reactor were heated to an internal temperature of 185° C. under normal pressure, and the BIBH tar and diethylenetriamine were reacted for 4 hours while stirring to obtain a polyamine composition containing 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane (reaction step).

[0196] During the reaction step, the concentrations of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane in the mixture of BIBH tar and diethylenetriamine were measured by gas chromatography at regular intervals, and the reaction step was terminated when the concentrations of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane no longer changed.

[0197] At the time of completion of the reaction step, the yield of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane was 62.60%.

[0198] Next, the obtained polyamine composition was cooled to an internal temperature of 145° C., and 16.43 parts by mass of granular sodium hydroxide was added to the cooled polyamine composition, followed by stirring for 3 hours to decompose the imidazolidinone in the polyamine composition.

[0199] Next, the polyamine composition was filtered under reduced pressure, and the filter residue was washed twice with 12.00 parts by mass of methanol.

[0200] Next, methanol was distilled off from the filtrate using an evaporator. The concentrations of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane in the filtrate after distillation of methanol were measured by gas chromatography, and the yield was calculated using the above formula. The yield of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane was 56.65%.

[0201] (3) Example 3

[0202] 5.00 parts by mass of XDI tar was placed in the reactor. Subsequently, 13.54 parts by mass of dipropylene triamine was added dropwise to the reactor at room temperature over 10 minutes to mix the XDI tar and dipropylene triamine.

[0203] Next, the XDI tar and dipropylene triamine in the reactor were heated to an internal temperature of 185° C. at normal pressure and reacted with stirring for 4 hours to obtain a polyamine composition containing xylylenediamine (polyamine compound) (reaction step).

[0204] It should be noted that in this example, in the reaction step, pyrimidinone (specifically, 1-(3-aminopropyl)tetrahydropyrimidin-2(1H)-one) was produced as a by-reaction instead of imidazolidinone.

[0205] During the reaction step, the concentration of xylylenediamine in the mixture of XDI tar and dipropylenetriamine was measured by gas chromatography at regular intervals, and the reaction step was terminated when the concentration of xylylenediamine stopped changing.

[0206] At the time point when the reaction step was completed, the yield of xylylenediamine was 61.24%.

[0207] (4) Example 4

[0208] The tar component (isocyanurate composition, hereinafter referred to as 1,3-BIC tar) obtained in the detarring step of Production Example 3 was prepared (preparation step).

[0209] The tar components were analyzed by infrared spectroscopy. The results showed that the 1690 cm -1 Therefore, it is estimated that the tar component contains a compound containing an isocyanurate skeleton.

[0210] 5.00 parts by mass of 1,3-BIC tar was placed in the reactor. Subsequently, 10.64 parts by mass of diethylenetriamine was added dropwise to the reactor at room temperature over 10 minutes to mix the 1,3-BIC tar and diethylenetriamine.

[0211] Next, the 1,3-BIC tar and diethylenetriamine in the reactor were heated to an internal temperature of 185° C. under normal pressure and reacted with stirring for 4 hours to obtain a polyamine composition containing 1,3-bis(aminomethyl)cyclohexane (reaction step).

[0212] During the reaction step, the concentration of 1,3-bis(aminomethyl)cyclohexane in the mixture of 1,3-BIC tar and dipropylenetriamine was measured by gas chromatography at regular intervals. The reaction step was terminated when the concentration of 1,3-bis(aminomethyl)cyclohexane stopped changing.

[0213] At the time point when the reaction step was completed, the yield of 1,3-bis(aminomethyl)cyclohexane was 44.51%.

[0214] (5) Comparative Example 1

[0215] 5.00 parts by mass of XDI tar was placed in the reactor. Next, 10.26 parts by mass of n-butylamine was added to the reactor at room temperature to mix the XDI tar and n-butylamine.

[0216] Next, the XDI tar and n-butylamine in the reactor were heated to an internal temperature of 80° C. (a temperature at which n-butylamine refluxes) at normal pressure, and stirred for 4 hours (reaction step).

[0217] During the reaction step, the concentration of xylylenediamine in the mixture of XDI tar and diethylenetriamine was measured by gas chromatography at regular intervals, but the generation of xylylenediamine was not detected (yield: 0.00%).

[0218] (6) Comparative Example 2

[0219] 5.00 parts by mass of XDI tar was placed in the reactor. Next, 8.43 parts by mass of ethylenediamine was added to the reactor at room temperature to mix the XDI tar and ethylenediamine.

[0220] Next, the XDI tar and ethylenediamine in the reactor were heated to an internal temperature of 120° C. (a temperature at which ethylenediamine refluxes) at normal pressure, and stirred for 4 hours (reaction step).

[0221] During the reaction step, the concentration of xylylenediamine in the mixture of XDI tar and ethylenediamine was measured by gas chromatography at regular intervals, and the reaction step was terminated when the concentration of xylylenediamine stopped changing.

[0222] At the time point when the reaction step was completed, the yield of xylylenediamine was 1.34%.

[0223] It should be noted that the above invention is provided as an exemplary embodiment of the present invention, but it is only for illustration and is not to be construed as limiting. Modifications of the present invention that are obvious to those skilled in the art are encompassed by the appended claims.

[0224] Industrial applicability

[0225] The method for producing a polyamine compound of the present invention can be used for producing a polyamine compound.

Claims

1. A method for producing a polyamine compound, comprising the following steps: a preparation step of preparing an isocyanurate composition containing an isocyanurate compound; and In the reaction step, the isocyanurate compound is reacted with a compound represented by the following general formula to obtain a polyamine compound. general formula: [Chemical Formula 1] In the above general formula, n is 1 or 2; R1 represents an amino group or a hydroxyl group; and R2 is a linear or branched hydrocarbon group having 1 to 10 carbon atoms, which may be substituted by an amino group or a hydroxyl group.

2. The method for producing a polyamine compound according to claim 1, wherein The isocyanurate composition further contains a polyisocyanate compound.

3. The method for producing a polyamine compound according to claim 2, wherein The polyisocyanate compound is produced by a production method comprising the following steps: an isocyanate formation step of reacting the polyamine compound with phosgene to obtain a reaction product containing the polyisocyanate compound; and a detarring step to remove tar components from the reaction product; The isocyanurate composition is the tar component removed in the detarring step.

4. The method for producing a polyamine compound according to claim 2 or 3, wherein The polyisocyanate compound is at least one selected from the group consisting of xylylenediisocyanate, bis(isocyanatemethyl)bicyclo[2,2,1]heptane, and bis(isocyanatemethyl)cyclohexane.

5. The method for producing a polyamine compound according to claim 4, wherein The polyisocyanate compound is xylylenediisocyanate.

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