WO2024190689A1 - Method for producing polyamine compound - Google Patents

Abstract

This method for producing a polyamine compound comprises: a preparation step for preparing an isocyanurate composition which contains an isocyanurate compound; and a reaction step for reacting the isocyanurate compound with a compound represented by a general formula to obtain a polyamine compound.　(In the general formula, n is 1 or 2. R₁ represents an amino group or a hydroxy group. R₂ is a C1-10 straight-chain or branched hydrocarbon group and may be substituted with an amino group or a hydroxy group.)

Description

Method for producing polyamine compound

The present invention relates to a method for producing a polyamine compound.

　Traditionally, polyamine compounds are known as raw materials for polyisocyanate compounds.

For example, xylylenediisocyanate is produced by reacting xylylenediamine hydrochloride with carbonyl chloride (see Patent Document 1 below).

International Publication No. 2018/190290

There is a demand for an efficient production of polyamine compounds that can be used for the production of polyisocyanate compounds such as those described in Patent Document 1.

The present invention provides a method for producing polyamine compounds that can efficiently produce polyamine compounds.

The present invention [1] includes a method for producing a polyamine compound, which includes 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.

General formula:

(In the above general formula, n is 1 or 2. _R1 represents an amino group or a hydroxy group. _R2 represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with an amino group or a hydroxy group.)
The present invention [2] includes the method for producing a polyamine compound according to the above [1], wherein the isocyanurate composition further contains a polyisocyanate compound.

The present invention [3] includes the method for producing a polyamine compound according to [2] above, in which the polyisocyanate compound is produced by a production method including an isocyanation step of reacting the polyamine compound with carbonyl chloride to obtain a reaction product containing the polyisocyanate compound, and a detarring step of removing tar components from the reaction product, and the isocyanurate composition is the tar components removed by the detarring step.

The present invention [4] includes the method for producing a polyamine compound according to the above [2] or [3], wherein the polyisocyanate compound is at least one selected from the group consisting of xylylene diisocyanate, bis(isocyanatomethyl)bicyclo[2,2,1]heptane, and bis(isocyanatomethyl)cyclohexane.
The present invention [5] includes the method for producing a polyamine compound according to the above [4], wherein the polyisocyanate compound is xylylene diisocyanate.

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

This allows the isocyanurate compound to be decomposed efficiently to obtain a polyamine compound.

As a result, polyamine compounds can be produced efficiently.

In the method for producing a polyamine compound of the present invention, for example, a tar component produced in the production of a polyisocyanate composition is used as a raw material to produce a polyamine compound by decomposing the isocyanurate compound in the tar component.

First, we will explain how to manufacture the polyisocyanate composition.

1. Method for Producing Polyisocyanate Composition The polyisocyanate composition contains a polyisocyanate compound as a main component.

Examples of polyisocyanate compounds include polyisocyanates that are widely used industrially. Examples of polyisocyanates include linear aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and aromatic aliphatic polyisocyanates.

Examples of linear aliphatic polyisocyanates include pentamethylene diisocyanate (PDI) and hexamethylene diisocyanate (HDI).

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

Examples of aromatic polyisocyanates include tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI).

Examples of aromatic aliphatic polyisocyanates include xylylene diisocyanate (XDI) and tetramethyl xylylene diisocyanate (TMXDI).

As the polyisocyanate compound, preferably, linear aliphatic polyisocyanates, alicyclic polyisocyanates, and aromatic aliphatic polyisocyanates are used, more preferably, xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), bis(isocyanatomethyl)bicyclo[2,2,1]heptane (BIBH), hexamethylene diisocyanate (HDI), pentamethylene diisocyanate (PDI), bis(isocyanatomethyl)cyclohexane (BIC), and hydrogenated diphenylmethane diisocyanate (H ₁₂ MDI) are used, and further preferably, xylylene diisocyanate (XDI), bis(isocyanatomethyl)bicyclo[2,2,1]heptane (BIBH), and bis(isocyanatomethyl)cyclohexane (BIC) are used. Xylylene diisocyanate has two structural isomers, 1,3-xylylene diisocyanate and 1,4-xylylene diisocyanate. Preferably, xylylene diisocyanate is 1,3-xylylene diisocyanate. Bis(isocyanatomethyl)cyclohexane has two structural isomers, 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane. Preferably, bis(isocyanatomethyl)cyclohexane is 1,3-bis(isocyanatomethyl)cyclohexane (1,3-BIC).

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, and is, for example, 99.95% by mass or less. Preferably, the polyisocyanate composition contains only the polyisocyanate compound.

When the polyisocyanate compound is xylylene diisocyanate, the content of xylylene diisocyanate in the polyisocyanate composition can be measured by the method described in paragraphs [0376] and [0377] of WO 2018/190290.

The method for producing a polyisocyanate composition includes a salt production process, an isocyanate formation process, a degassing process, a desolvation process, a detarring process, and a purification process. The method for producing a polyisocyanate composition sequentially carries out a salt production process, an isocyanate formation process, a degassing process, a desolvation process, a detarring process, and a purification process.

(1) Salt formation process In the salt formation process, for example, a polyamine compound and hydrogen chloride are mixed in the presence of an inert solvent. More specifically, in the salt formation process, hydrogen chloride gas is first introduced into an inert solvent, and then a polyamine solution in which a polyamine compound is dissolved in an inert solvent is supplied to the inert solvent into which hydrogen chloride gas has been introduced. Then, the inert solvent, the polyamine compound, and hydrogen chloride are mixed. This produces a slurry containing the hydrochloride of the polyamine compound.

Examples of the polyamine compound include polyamines corresponding to the polyisocyanate compounds described above. Examples of the polyamine compound include linear aliphatic polyamines, alicyclic polyamines, aromatic polyamines, and aromatic aliphatic polyamines.

Examples of chain aliphatic polyamines include pentamethylenediamine and hexamethylenediamine.

Examples of alicyclic polyamines include isophorone diamine, bis(aminomethyl)bicyclo[2,2,1]heptane, hydrogenated diphenylmethane diamine, and bis(aminomethyl)cyclohexane (BAC).

Examples of aromatic polyamines include tolylenediamine and diphenylmethanediamine.

Examples of aromatic aliphatic polyamines include xylylenediamine and tetramethylxylylenediamine.

When the polyisocyanate compound is 1,3-xylylene diisocyanate, the polyamine compound is 1,3-xylylene diamine. When the polyisocyanate compound is bis(isocyanatomethyl)bicyclo[2,2,1]heptane, the polyamine compound is bis(aminomethyl)bicyclo[2,2,1]heptane. When the polyisocyanate compound is 1,3-bis(isocyanatomethyl)cyclohexane, the polyamine compound is 1,3-bis(aminomethyl)cyclohexane (1,3-BAC).

Examples of inert solvents include aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, halogenated aromatic hydrocarbons, nitrogen-containing compounds, ethers, ketones, fatty acid esters, and aromatic carboxylate esters.

Aromatic hydrocarbons include, for example, benzene, toluene, and xylene.

Examples of aliphatic hydrocarbons include octane and decane.

Examples of alicyclic hydrocarbons include cyclohexane, methylcyclohexane, and ethylcyclohexane.

Halogenated aromatic hydrocarbons include, for example, chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene.

Examples of nitrogen-containing compounds include nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N'-dimethylimidazolidinone.

Ethers include, for example, dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether.

Ketones include, for example, heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl ketone.

Fatty acid esters include, for example, ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate.

Examples of aromatic carboxylic acid esters include methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate.

The inert solvents can be used alone or in combination of two or more types.

Preferably, the inert solvent is a halogenated aromatic hydrocarbon, more preferably, chlorobenzene or dichlorobenzene.

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% by mass or more, preferably 5.0% by mass or more, and for example, 30% by mass or less, preferably 20% by mass or less.

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

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

The temperature of the salt production process 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.

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

(2) Isocyanate Process In the isocyanate process, the hydrochloride of the polyamine compound is reacted with carbonyl chloride (hydrochloride method). Specifically, in the isocyanate process, the hydrochloride of the polyamine compound is reacted with carbonyl chloride by supplying carbonyl chloride to the slurry obtained in the salt formation process. This produces a reaction product containing a polyisocyanate compound.

The supply ratio of carbonyl chloride 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, per 1 mol of the hydrochloride salt of the polyamine compound.

The duration of the isocyanation process is, for example, 4 hours or more, preferably 6 hours or more, and, for example, 25 hours or less, preferably 20 hours or less, more preferably 15 hours or less.

The temperature of the isocyanation process is, for example, 90°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and, for example, 190°C or lower, preferably 180°C or lower, more preferably 160°C or lower.

The pressure (gauge pressure) in the isocyanation process is, for example, in excess of atmospheric pressure (0 MPaG), preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, even more preferably 0.003 MPaG or more, particularly preferably 0.01 MPaG (10 kPaG) or more, particularly preferably 0.02 MPaG (20 kPaG) or more, most preferably 0.03 MPaG (30 kPaG) or more, and is, for example, 0.6 MPaG or less, preferably 0.4 MPaG or less, more preferably 0.2 MPaG or less.

The isocyanation process is preferably carried out in a continuous manner. That is, in the isocyanation process, the slurry obtained in the salt formation process is continuously transferred from the vessel used in the salt formation process to the reaction vessel used in the isocyanation process, and the hydrochloride of the polyamine compound and the carbonyl chloride are reacted in the reaction vessel, while the resulting reaction product (reaction mass) is continuously removed from the reaction vessel.

In the isocyanation process, carbamoyl chloride is produced by the reaction of a polyamine compound with carbonyl chloride, and a polyisocyanate compound is produced by the decomposition reaction of carbamoyl chloride.

In the isocyanation process, the polyisocyanate compound produced reacts with the intermediate carbamoyl chloride to produce an isocyanurate compound as a by-product.

If we take the case where the polyamine compound is xylylenediamine as an example, as shown in reaction formula (1) below, two molecules of xylylenediisocyanate react with one molecule of carbamoyl chloride to produce one molecule of isocyanurate compound and one molecule of chloromethylbenzylisocyanate as by-products.

Reaction formula (1)

(3) Degassing Step In the degassing step, excess carbonyl chloride and by-product gases such as hydrogen chloride are removed from the reaction product using a known degassing tower.

(4) Solvent Removal Step In the solvent removal step, the inert solvent is distilled off from the reaction product using a known distillation column.

(5) Detarring Step In the detarring step, tar components are removed from the reaction product using a known detarring device.

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

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

In the detarring process, some of the polyisocyanate compounds in the reaction product are extracted from the reaction product as tar components together with the isocyanurate compounds. Therefore, the tar components contain polyisocyanate compounds.

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

(6) Purification Step In the purification step, the reaction product after the detarring step is purified to adjust the content of the polyisocyanate compound to the above range.

Examples of purification methods include crystallization and distillation, and preferably distillation. To purify the reaction product by distillation, for example, low boiling materials (low boiling point components) are distilled from the reaction product, and the reaction product after the low boiling materials are distilled is then rectified. In other words, the purification process includes a low boiling removal process in which the low boiling materials are distilled from the reaction product, and a rectification process in which the reaction product after the low boiling materials are distilled is rectified.

2. Method for Producing Polyamine Compound Next, a method for producing a polyamine compound will be described.

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

(1) Preparation Step In the preparation step, an isocyanurate composition is prepared. In this embodiment, the isocyanurate composition is a tar component removed by a detarring step in the production of a polyisocyanate composition. Therefore, the isocyanurate composition contains the isocyanurate compound in the above reaction formula (1) and a polyisocyanate compound.

(2) Reaction Step In the reaction step, the isocyanurate composition is mixed with a compound represented by the following general formula and heated, thereby reacting the isocyanurate compound and the polyisocyanate compound with the compound represented by the following general formula.

General formula:

In the above general formula, n is 1 or 2. In the above general formula, R1 represents an amino group or a hydroxy group.

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

Examples of linear or branched hydrocarbon groups 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.

Examples of linear or branched aliphatic hydrocarbon groups 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.

Examples of linear alkyl groups 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 groups.

Examples of branched alkyl groups having 3 to 12 carbon atoms include isopropyl, isobutyl, sec-butyl, tert-butyl, and 2-ethylhexyl groups.

Examples of aromatic hydrocarbon groups having 6 to 10 carbon atoms include phenyl and naphthyl groups.

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

Specific examples of the compound represented by the above general formula when n is 1 include diethylenetriamine, N-methylethylenediamine, N-phenylethylenediamine, and diethanolamine. Specific examples of the compound represented by the above general formula when n is 2 include dipropylenetriamine and dipropanolamine. Preferred examples of the compound represented by the following general formula include diethylenetriamine and dipropylenetriamine.

The boiling point at 1 atmosphere of the compound represented by the above general formula is, 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.

The compound represented by the above general formula is mixed with 1 mol of the isocyanurate compound 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.

The heating temperature in the reaction process 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.

The heating time in the reaction step is, for example, 1 hour or more, preferably 3 hours or more, and, for example, 10 hours or less, preferably 8 hours or less.

In the reaction process, the isocyanurate compound is decomposed by the compound represented by the above general formula to produce a polyamine compound. In the above general formula, when n is 1 and R1 is an amino group, imidazolidinone is by-produced in the reaction process. In addition, in the above general formula, when n is 1 and R1 is a hydroxy group, oxazolidinone is by-produced instead of imidazolidinone. In addition, in the above general formula, when n is 2 and R1 is an amino group, tetrahydropyrimidinone is by-produced instead of imidazolidinone in the reaction process. In addition, in the above general formula, when n is 2 and R1 is a hydroxy group, oxazinanone is by-produced instead of imidazolidinone in the reaction process.

As an example, when the isocyanurate composition is a tar component produced in the production of xylylene diisocyanate and the compound represented by the above general formula is diethylenetriamine, as shown in the following reaction formula (2), the isocyanurate compound reacts with diethylenetriamine to produce xylylenediamine and imidazolidinone (more specifically, 3-aminoethyl-2-imidazolidinone). Also, as shown in the following reaction formula (3), xylylene diisocyanate in the tar component reacts with diethylenetriamine to produce xylylenediamine and imidazolidinone.

Reaction scheme (2):

 

Reaction scheme (3):

When the isocyanurate composition is a tar component produced in the production of xylylene diisocyanate and the compound represented by the above general formula is dipropylene triamine, the isocyanurate compound reacts with dipropylene triamine to produce xylylene diamine and tetrahydropyrimidinone (specifically, 1-(3-aminopropyl)tetrahydropyrimidin-2(1H)-one) as shown in the following reaction formula (4). Also, the xylylene diisocyanate in the tar component reacts with dipropylene triamine to produce xylylene diamine and tetrahydropyrimidinone as shown in the following reaction formula (5).
Reaction formula (4):

Reaction formula (5):

By decomposing an isocyanurate compound with the compound represented by the above general formula, the isocyanurate compound can be decomposed in a simple process of heating at normal pressure, and a polyamine compound can be efficiently produced.

Then, the reaction liquid obtained in the reaction step may be heated with, for example, sodium hydroxide added thereto to decompose the imidazolidinone. The decomposition of imidazolidinone produces diethylenetriamine.

In addition, the reaction liquid obtained in the reaction step is distilled and rectified to obtain a xylylenediamine composition containing xylylenediamine.

The content of xylylenediamine in the xylylenediamine 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, and is, for example, 99.95% by mass or less, preferably 99.90% by mass or less.

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

3. Effects and Effects According to the method for producing a polyamine compound, in the reaction step, an isocyanurate compound is reacted with the specific compound represented by the above general formula.

This allows the isocyanurate compound to be decomposed efficiently to obtain a polyamine compound.

As a result, polyamine compounds can be produced efficiently.

In addition, if the tar components generated in the production of the polyisocyanate composition are used as the raw material isocyanurate composition, the raw material costs for the production of the polyamine compound can be reduced.

Furthermore, if polyamine compounds produced from tar components are used in the production of polyisocyanate compositions, the raw material costs involved in the production of polyisocyanate compositions can also be reduced.

In addition, if the tar component is used as an isocyanurate composition, the amount of tar component generated in the production of the polyisocyanate composition that is discarded can be reduced. This reduces the environmental impact caused by the disposal of the tar component.

In addition, if a tar component is used as an isocyanurate composition, a polyamine compound can also be produced from the polyisocyanate compound in the tar component.

This prevents polyisocyanate compounds from being disposed of as tar components.

4. Modifications The method of isocyanation in the production of the polyisocyanate composition is not limited to the hydrochloride method described above. The isocyanation step can also be carried out using a cold/hot two-stage method or a phosgene pressure method.

When the isocyanation process is carried out using a two-stage cold/hot method, first, a polyamine compound is dissolved in the inert solvent described above to obtain a polyamine solution. Next, carbonyl chloride is introduced into the polyamine solution in an amount 5 to 20 times the molar amount of the polyamine compound, and the polyamine compound and carbonyl chloride are reacted at, for example, 0 to 90°C (first-stage reaction). Next, the polyamine compound is reacted with carbonyl chloride in the presence of about 0.5 to 10 times the molar amount of the polyamine compound, for example, at 100 to 150°C (second-stage reaction).

When the isocyanation process is carried out using the phosgene pressurization method, the polyamine compound is heated to a temperature equal to or higher than the boiling point of the polyamine compound, and, for example, under a pressure of 100 to 500 kPa, carbonyl chloride in an amount 1 to 10 times the molar amount of the polyamine compound is introduced together with a carrier gas such as nitrogen or argon, and the polyamine compound and carbonyl chloride are reacted.

Even when the isocyanation process is carried out using the hot-cold two-stage method or the phosgene pressure method, tar components containing isocyanurate compounds are produced.

The isocyanurate composition may be a tar component produced in the production of a polyisocyanate composition using a hot-cold two-stage process or a phosgene pressurized process.

The isocyanurate composition is not limited to a tar component produced in the production of a polyisocyanate composition. The isocyanurate composition may be, for example, a distillation residue produced in the purification step of the production of a polyisocyanate composition. In particular, the isocyanurate composition may be a distillation residue produced in the rectification of the reaction product after the low boiling points are distilled off in the purification step described above. The isocyanurate composition may also be a mixture of a tar component and a distillation residue produced in the purification step.

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

The present invention is described in more detail below with examples, but is not limited thereto. Specific numerical values of the compounding ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values (numerical values defined as "equal to or less than") or lower limit values (numerical values defined as "equal to or more than" or "exceeding") of the corresponding compounding ratio (content ratio), physical property values, parameters, etc. described in the above "Form for carrying out the invention." Note that "parts" and "%" are based on mass unless otherwise specified.

1. Production of polyisocyanate composition (1) Production Example 1 (Production of XDI composition)
An XDI composition was produced under the conditions of Example 2 of WO 2018/190290. In addition, in the step of detarring the desolvated mass to prepare a detarred mass (detarring step), specifically, the detarred mass was prepared by removing tar components from the desolvated mass (detarring).

(2) Production Example 2 (Production of BIBH Composition)
An autoclave (inner volume 2 m ³ ) equipped with a reflux condenser, stirring blade, thermometer, hydrogen chloride gas inlet tube, carbonyl chloride inlet tube, raw material tank, raw material charging pump and a pressure regulator was used as a reactor.

958 g of orthodichlorobenzene was charged into the reactor as the reaction solvent, and 154.2 g (1.0 mole) 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 orthodichlorobenzene (inert solvent) were charged into the raw material tank (total amine concentration 8.5% by mass).

Next, the temperature inside the reactor was raised to 120°C, and the autoclave was adjusted to a pressure 0.01 MPa higher than atmospheric pressure. Hydrogen chloride gas was then started to be fed into the reactor from the hydrogen chloride gas inlet tube at a rate of 43.8 g/hr. At the same time, 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 started to be fed from the raw material tank at a rate of 428.1 g/hr using the raw material feeding pump, and the entire amount was fed over 2 hours. Hydrogen chloride gas was further fed at 20 g/hr while maturing for 1 hour. As a result, a hydrochloride slurry containing 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane hydrochloride was obtained (salt production process).

Next, the hydrochloride slurry was heated to 160°C in the reactor, and carbonyl chloride was blown in at 100g/hr (1.0 mol/hr) from the carbonyl chloride inlet tube, and the reaction was carried out for 8 hours while maintaining the temperature. This resulted in a reaction product containing 2,5-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (polyisocyanate compound) and 2,6-bis(isocyanatomethyl)bicyclo[2.2.1]heptane (polyisocyanate compound) (isocyanation process).

After the reaction was completed, unreacted phosgene and hydrogen chloride gas were removed by purging nitrogen into the system (degassing process). The reaction liquid was then filtered to remove 0.5 g (dry mass) of unreacted hydrochloride.

Ortho-dichlorobenzene was removed from the obtained filtrate (solvent removal process), and tar components were removed (tar removal process), yielding 206.9 g of a BIBH composition with a BIBH purity of 98.5% by mass.

Next, the obtained BIBH composition was rectified to obtain a BIBH composition with a BIBH purity of 99.99 mass% (purification step).
(3) Production Example 3 (Production of 1,3-BIC composition)
Except for replacing the mixture of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane with 1,3-bis(aminomethyl)cyclohexane (polyamine compound), the salt formation step, isocyanation step, degassing step, desolvation step, detarring step and purification step were carried out in the same manner as in Production Example 2, to obtain a 1,3-BIC composition containing 1,3-bis(isocyanatomethyl)cyclohexane (polyisocyanate compound).

2. Production of polyamine compound (1) Example 1
A tar component (isocyanurate composition, hereinafter referred to as XDI tar) removed from the solvent-removed mass in the detarring step of Production Example 1 was prepared (preparation step).
When the tar components were analyzed by infrared spectroscopy, a peak was observed in the vicinity of 1690 cm ⁻¹ in the infrared absorption spectrum, similar to that of cyanuric acid. Therefore, it was speculated that the tar components contained a compound containing an isocyanurate skeleton.

Next, 50.00 parts by mass of XDI tar was charged into the reactor. Next, 144.73 parts by mass of diethylenetriamine was dripped into the reactor at room temperature over a period of 10 minutes to mix the XDI tar and diethylenetriamine.

Next, the XDI tar and diethylenetriamine in the reactor were heated at normal pressure until the internal temperature reached 185°C, and the XDI tar and diethylenetriamine were reacted with each other for 6 hours while stirring to obtain a polyamine composition containing xylylenediamine (polyamine compound) (reaction process).

During the reaction process, the concentration of xylylenediamine in the mixture of XDI tar and diethylenetriamine was measured at regular intervals using gas chromatography, and the reaction process was terminated when the concentration of xylylenediamine no longer changed. The gas chromatography measurement conditions are shown below.

<Gas Chromatography Measurement Conditions>
Equipment: SHIMADZU GC-2014
Column: DB-1 (film thickness 1.5 μm, inner diameter 0.53 mm × length 60 m, manufactured by Agilent)
Oven temperature: hold at 50°C for 2 minutes, increase temperature from 50°C to 150°C at 10°C/min, hold for 5 minutes after reaching 150°C, increase temperature from 150°C to 300°C at 10°C/min, hold for 10 minutes after reaching 300°C.

Injection method: Pulsed splitless method Injection port temperature: 250°C
Detector temperature: 300°C
Carrier gas: _N2 158 kPa, _H2 55 kPa, Air 45 kPa (constant pressure control)
Internal standard: 2,2,6,6-tetramethylpiperidine 50 mg
Solvent: 1:1 mixture of dichloromethane and methanol Sample concentration: 50 mg/5 mL
Injection volume: 1 μL
Detection method: FID
The molar amount of xylylenediamine obtained from the gas chromatography was converted to mass to calculate the yield of xylylenediamine. The retention time of xylylenediamine was 25.2 minutes.

At the end of the reaction process, the yield of xylylenediamine was 50.02%. The yield can be calculated using the following formula:

Yield=mass of produced polyamine compound/mass of tar component×100
Next, the obtained polyamine composition was cooled until the internal temperature reached 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, thereby decomposing the imidazolidinone in the polyamine composition.

The polyamine composition was then filtered under reduced pressure. The filtered residue was washed twice with 30.00 parts by mass of methanol.

Next, an evaporator was used to distill off methanol from the filtrate. The concentration of xylylenediamine in the filtrate after the methanol had been distilled off was measured using gas chromatography, and the yield was calculated using the above formula, resulting in a xylylenediamine yield of 44.62%.

Then, the filtrate after removing the methanol was distilled under reduced pressure to obtain a mixture of xylylenediamine and diethylenetriamine as the distillate.

The concentration of xylylenediamine in the fraction was measured using gas chromatography, and the yield was calculated using the above formula, resulting in a yield of 37.84%.

(2) Example 2
A tar component (isocyanurate composition, hereinafter referred to as BIBH tar) obtained in the detarring step of Production Example 2 was prepared (preparation step).
When the tar components were analyzed by infrared spectroscopy, a peak was observed in the vicinity of 1690 cm ⁻¹ in the infrared absorption spectrum, and it was therefore presumed that the tar components contained a compound containing an isocyanurate skeleton.

Next, 20.00 parts by mass of BIBH tar was charged into the reactor. Next, 73.81 parts by mass of diethylenetriamine was dripped into the reactor at room temperature over a period of 10 minutes to mix the XDI tar and diethylenetriamine.

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 with 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 process).

During the reaction process, 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 at regular intervals using gas chromatography, and the reaction process 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.

At the end of the reaction process, 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%.

Then, the obtained polyamine composition was cooled until the internal temperature reached 145°C, and 16.43 parts by mass of granular sodium hydroxide was added to the cooled polyamine composition and stirred for 3 hours. This decomposed the imidazolidinone in the polyamine composition.

The polyamine composition was then filtered under reduced pressure. The filtered residue was washed twice with 12.00 parts by mass of methanol.

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 methanol was distilled off were measured using gas chromatography, and the yield was calculated using the above formula, resulting in a yield of 2,5-bis(aminomethyl)bicyclo[2.2.1]heptane and 2,6-bis(aminomethyl)bicyclo[2.2.1]heptane of 56.65%.
(3) Example 3
5.00 parts by mass of XDI tar was charged into the reactor. Next, 13.54 parts by mass of dipropylene triamine was dropped into the reactor at room temperature over 10 minutes to mix the XDI tar and the dipropylene triamine.
Next, the XDI tar and dipropylene triamine in the reactor were heated to an internal temperature of 185°C under normal pressure, and the XDI tar and dipropylene triamine were reacted with each other for 4 hours while stirring to obtain a polyamine composition containing xylylene diamine (polyamine compound) (reaction process).
In this example, pyrimidinone (specifically, 1-(3-aminopropyl)tetrahydropyrimidin-2(1H)-one) was produced as a by-product in place of imidazolidinone in the reaction step.
During the reaction process, the concentration of xylylenediamine in the mixture of XDI tar and dipropylenetriamine was measured by gas chromatography at regular time intervals, and the reaction process was terminated when the concentration of xylylenediamine no longer changed.
At the end of the reaction process, the yield of xylylenediamine was 61.24%.
(4) Example 4
A 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).
When the tar components were analyzed by infrared spectroscopy, a peak was observed in the vicinity of 1690 cm ⁻¹ in the infrared absorption spectrum, and it was therefore presumed that the tar components contained a compound containing an isocyanurate skeleton.
5.00 parts by mass of 1,3-BIC tar was charged into the reactor, and then 10.64 parts by mass of diethylenetriamine was dropped into the reactor at room temperature over 10 minutes to mix the 1,3-BIC tar and diethylenetriamine.
Next, the 1,3-BIC tar and diethylenetriamine in the reactor were heated to an internal temperature of 185° C. under normal pressure, and the 1,3-BIC tar and diethylenetriamine were reacted with each other for 4 hours while stirring to obtain a polyamine composition containing 1,3-bis(aminomethyl)cyclohexane (reaction step).
During the reaction process, 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 time intervals, and the reaction process was terminated when the concentration of 1,3-bis(aminomethyl)cyclohexane no longer changed.
At the end of the reaction process, the yield of 1,3-bis(aminomethyl)cyclohexane was 44.51%.

(5) Comparative Example 1
5.00 parts by mass of XDI tar was charged into the reactor. Next, 10.26 parts by mass of n-butylamine was added to the reactor at room temperature, and the XDI tar and n-butylamine were mixed.

Next, the XDI tar and n-butylamine in the reactor were heated at normal pressure until the internal temperature reached 80°C (the temperature at which n-butylamine refluxes), and then stirred for 4 hours (reaction process).

During the reaction process, the concentration of xylylenediamine in the mixture of XDI tar and diethylenetriamine was measured at regular intervals using gas chromatography, but no production of xylylenediamine was detected (yield: 0.00%).

(6) Comparative Example 2
5.00 parts by mass of XDI tar was charged into the reactor. Next, 8.43 parts by mass of ethylenediamine was added to the reactor at room temperature, and the XDI tar and ethylenediamine were mixed.

Next, the XDI tar and ethylenediamine in the reactor were heated at normal pressure until the internal temperature reached 120°C (the temperature at which ethylenediamine refluxes) and stirred for 4 hours (reaction process).

During the reaction process, the concentration of xylylenediamine in the mixture of XDI tar and ethylenediamine was measured using gas chromatography at regular intervals, and the reaction process was terminated when the concentration of xylylenediamine no longer changed.

At the end of the reaction process, the yield of xylylenediamine was 1.34%.
The above invention is provided as an exemplary embodiment of the present invention, but this is merely an example and should not be interpreted as being limited. Modifications of the present invention that are obvious to those skilled in the art are included in the scope of the following claims.

The method for producing a polyamine compound of the present invention is utilized for producing a polyamine compound.

Claims (5)

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.
General formula:

(In the above general formula, n is 1 or 2. _R1 represents an amino group or a hydroxy group. _R2 represents a linear or branched hydrocarbon group having 1 to 10 carbon atoms, which may be substituted with an amino group or a hydroxy group.) The method for producing a polyamine compound according to claim 1, wherein the isocyanurate composition further contains a polyisocyanate compound. The polyisocyanate compound is
an isocyanation step of reacting the polyamine compound with carbonyl chloride to obtain a reaction product containing the polyisocyanate compound;
and a detarring step of removing a tar component from the reaction product,
The method for producing a polyamine compound according to claim 2 , wherein the isocyanurate composition is the tar component removed in the detarring step. The method for producing a polyamine compound according to claim 2 or 3, wherein the polyisocyanate compound is at least one selected from xylylene diisocyanate, bis(isocyanatomethyl)bicyclo[2,2,1]heptane, and bis(isocyanatomethyl)cyclohexane. The method for producing a polyamine compound according to claim 4, wherein the polyisocyanate compound is xylylene diisocyanate.