JP2017178836A - Manufacturing method of polyalkylene polyamines - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method of a polyalkylene polyamine mixture high in abundance ratio of linear polyalkylene polyamine.SOLUTION: There is provided a manufacturing method of polyalkylene polyamine by reacting a raw material polyalkylene polyamine having a primary amino group with ethylene dichloride the raw material polyalkylene polyamine having the primary amino group is used at 4 mol equivalent to the ethylene dichloride and reaction is conducted in a temperature range of 100°C to 200°C.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing polyalkylene polyamines having high structure selectivity and high yield.

  The polyalkylene polyamine means one having a molecular structure in which primary, secondary, or tertiary amino groups are linked via an alkylene chain such as a methylene chain, an ethylene chain, or a propylene chain. Polyalkylene polyamines are known as compounds useful for epoxy resin curing agents, chelating agents, lubricants, raw materials for medicines and agricultural chemicals, for example.

  A typical method for producing a polyalkylene polyamine is a method in which a reaction is performed using monoethanolamine as a raw material in the presence of ammonia, hydrogen, and a catalyst (see, for example, Patent Document 1). In addition, a method using ethylenediamine or ethylene glycol (EG) as a raw material is also known (see, for example, Patent Document 2). These are methods by which polyalkylene polyamines having a relatively low molecular weight such as ethylenediamine (EDA) and diethylenetriamine (DETA) can be obtained with good yield. However, in the above method, the yield of polyalkylene polyamine having a relatively large molecular weight such as triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA) is not sufficient.

  Examples of a method for obtaining a high molecular weight polyalkylene polyamine include a method called an EDC method. Specifically, a method of reacting ammonia and ethylene dichloride (EDC) in the absence of a catalyst can be exemplified (for example, patents). Reference 3). However, the product by this method is generally a mixture (composition) of structural isomers of EDA, DETA, TETA, TEPA, PEHA, aminoethylpiperazine (AEP), and each polyalkylene polyamine. Examples of such structural isomers include linear, branched, and cyclic (for example, having a piperazine ring structure in the molecule) polyalkylene polyamine.

  A single composition polyalkylene polyamine and a mixture of structural isomers exhibit different performance in use. For example, linear TETA is effective in improving the glass transition temperature, which is one of the main physical properties of epoxy resins (see, for example, Patent Document 4). As described above, depending on the use of the polyalkylene polyamine, it is expected that a single composition or a composition close thereto exhibits higher performance than a mixture.

  However, these structural isomers become more diverse as the molecular weight of the polyalkylene polyamine increases, making selective synthesis difficult. In addition, since the chemical and physical properties of each isomer are similar, separation and purification requires a very advanced technique, and it is difficult to collect as a single compound. For example, PEHA is not a single chemical, but is marketed as a mixture of linear, branched, and cyclic isomers, and the selectivity of each isomer is low.

  On the other hand, a method of performing a reaction by changing the raw material in the EDC method from ammonia to DETA has been proposed (see, for example, Patent Document 5). However, according to this method, the addition time of the raw material and the reaction time are long, and it cannot be said that this method is practical.

  As described above, there is no industrial production method that can produce polyalkylene polyamines with high production efficiency and high structure selectivity by a method for producing polyalkylene polyamines.

JP 2009-510019 A JP 2009-510020 A International Publication No. 2007/042466 Pamphlet International Publication No. 2011/107512 Pamphlet JP-A-8-291111

  The present invention has been made in view of the above-described background art, and an object of the present invention is to provide polyalkylene polyamines having a high abundance ratio of linear polyalkylene polyamines and a production method for obtaining them in high yield. That is.

  As a result of intensive studies to solve the above problems, the present inventors have completed the present invention. That is, the present invention relates to the following polyalkylene polyamines and a method for producing the same.

  [1] A process for producing a polyalkylene polyamine in which a raw material polyalkylene polyamine having a primary amino group is reacted with ethylene dichloride, wherein the raw material polyalkylene polyamine having a primary amino group is used in an amount of 4 molar equivalents or more based on ethylene dichloride. The method for producing a polyalkylene polyamine mixture, wherein the reaction is performed in a temperature range of 100 ° C. or more and 200 ° C. or less.

  [2] The polyalkylene polyamine mixture according to [1], wherein the starting polyalkylene polyamine having a primary amino group is ethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, or N-aminoethylpiperazine. Production method.

  [3] The method for producing a polyalkylene polyamine mixture according to [1] or [2], wherein the starting polyalkylene polyamine having a primary amino group is ethylenediamine or diethylenetriamine.

  [4] The method for producing a polyalkylene polyamine mixture according to any one of [1] to [3], wherein the concentration of the starting polyalkylene polyamine having a primary amino group is 30% by weight or more.

  [5] The method for producing a triethylenetetramine mixture according to [1], wherein ethylenediamine is used in an amount of 4 molar equivalents or more with respect to ethylene dichloride, and the reaction is performed in a temperature range of 120 ° C to 180 ° C.

  [6] The method for producing a pentaethylenehexamine mixture according to [1], wherein diethylenetriamine is used in an amount of 8 molar equivalents or more with respect to ethylene dichloride, and the reaction is performed in a temperature range of 120 ° C. or higher and 180 ° C. or lower.

  Hereinafter, the present invention will be described in detail.

  In the present invention, a raw material polyalkylene polyamine having a primary amino group (hereinafter referred to as “raw material polyalkylene polyamine”) is reacted with ethylene dichloride to produce a polyalkylene polyamine mixture having a higher molecular weight than the raw material polyalkylene polyamine (hereinafter referred to as “polyalkylene polyamine”). , Referred to as “polyalkylene polyamine mixture”).

  In the present invention, examples of the raw material polyalkylene polyamine include ethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, and N-aminoethylpiperazine. In addition, substituted polyethylene polyamines such as N-methylethylenediamine, N-methylpropylenediamine, and N, N′-dimethylethylenediamine can also be used as a raw material. Among these, polyethylene polyamine is preferable, and inexpensive ethylenediamine and diethylenetriamine are particularly preferable.

  In the present invention, an excessive amount of the raw material polyalkylene polyamine (for example, ethylenediamine) may be present in order to suppress the sequential reaction of the resulting polyalkylene polyamine mixture (for example, a mixture of triethylenetetramine) and EDC. In order to obtain a polyalkylene polyamine mixture with a high yield, 4 equivalents or more of the raw material polyalkylene polyamine is required with respect to the number of moles of EDC. The equivalent or less is preferable.

  In the present invention, a solvent may be used when performing the reaction. Examples of the solvent include, but are not limited to, water, methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, glycerin, tetrahydrofuran, dioxane, acetonitrile, methoxyethanol, dimethoxyethane, DMF, DMSO, Benzene, toluene, xylene and the like can be used. These solvents can be used not only alone but also in combination of two or more as required. Of these, inexpensive water is preferred.

  As a reaction system in the present invention, either a flow system or a batch system may be adopted.

  In the present invention, the reaction temperature, reaction time, and reaction pressure are not particularly limited. Usually, the reaction temperature is from 80 ° C. to 250 ° C., the reaction time is from 10 minutes to 3 hours, and the reaction pressure is from normal pressure to 20 MPa. Is called. The reaction temperature is preferably 100 ° C. or higher and 200 ° C. or lower, more preferably 120 ° C. or higher and 180 ° C. or lower. When the reaction temperature is lower than 80 ° C., the reaction rate is extremely slow, which is not practical. When the reaction temperature is higher than 250 ° C., there is a problem that the deterioration of the apparatus due to decomposition or corrosion of the product is accelerated.

  In the present invention, the concentration of the raw material polyalkylene polyamine is not particularly limited, but it is preferably carried out at a concentration of 30% by weight or more in order to increase production efficiency.

  In the present invention, the reaction atmosphere is not particularly limited, and for example, the reaction is performed in air or in an inert atmosphere.

  After completion of the reaction, the target polyalkylene polyamine mixture is purified by distillation. At this time, in order to prevent deterioration of distillation efficiency, by-produced salts may be removed. Examples of the method for removing the by-product salt include a method for removing the salt by an operation such as distilling off the solvent, concentration, recrystallization, filtration, and centrifugation. Moreover, after distilling a solvent off, the method of extracting a polyalkylene polyamine mixture with another solvent, and removing a salt by centrifugation operation is also mentioned. The extracted polyalkylene polyamine mixture is purified by distillation under reduced pressure after distilling off the solvent. Although it does not specifically limit as distillation conditions, Usually, 180 to 230 degreeC and a pressure are performed in the range of 5 mmHg-20 mmHg. The recovered raw material polyalkylene polyamine may be used again as a raw material for producing the polyalkylene polyamine. At this time, the energy cost for raw material recovery can be reduced as the amine having a lower boiling point is the main fraction.

  According to the production method of the present invention, it is possible to obtain polyalkylene polyamines having a higher abundance ratio of linear polyalkylene polyamines than in the past in a high yield.

  The present invention will be described in more detail with reference to the following examples, but the present invention should not be construed as being limited thereto.

Example 1
A 70% by weight aqueous solution of ethylenediamine and ethylene dichloride were fed to a flow reactor heated to 150 ° C. in an oil bath using a metering pump so that the molar ratio of ethylenediamine / ethylene dichloride was 4, and the residence time was The reaction was performed in 25 minutes. The reaction solution that had flowed out was returned to room temperature, and then neutralized with a 48 wt% aqueous sodium hydroxide solution. Assignment of linear, branched, cyclic triethylenetetramine, and pentaethylenehexamine was performed by retention time and MS spectrum analysis in a gas chromatograph (GC). The evaluation results are shown in Table 1. The linear, branched, and cyclic ratios in Tables 1 and 2 mean the area ratio of each isomer in the total peak area attributed to triethylenetetramine and pentaethylenehexamine in the GC chart.

  As GC, GC-2025 manufactured by Shimadzu Corporation was used, and Agilent capillary column DB-1 manufactured by Agilent was used as the column. As a result of analyzing the product, the yield of triethylenetetramine was 62% by weight. The proportion of structural isomers of triethylenetetramine was 83% for the straight chain and 17% for the ring.

Examples 2-7
In Example 1, the reaction was performed in the same manner as in Example 1 except that the molar ratio of ethylenediamine / ethylene dichloride was changed to a range of 6-20. The results are shown in Table 1.

Examples 8-9
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 120 ° C and 180 ° C. The results are shown in Table 1.

Examples 10-13
In Example 1, the reaction was performed in the same manner as in Example 1 except that the aqueous concentration of ethylenediamine was changed to a range of 30% to 60% by weight. The results are shown in Table 1.

Examples 14-16
In Example 1, the reaction was performed in the same manner as in Example 1 except that a 50% by weight aqueous solution of diethylenetriamine was used instead of the 70% by weight aqueous solution of ethylenediamine, and the molar ratio was changed. The results are shown in Table 2.

Comparative Example 1
In Example 1, a reaction was performed in the same manner as in Example 1 except that a 20% by weight aqueous solution of ammonia was used instead of the 70% by weight aqueous solution of ethylenediamine and the molar ratio of ammonia / ethylene dichloride was changed to 4. . The results are shown in Table 3.

Comparative Examples 2-5
In Comparative Example 1, the reaction was performed in the same manner as in Comparative Example 1 except that the molar ratio of ammonia / ethylene dichloride was changed to the range of 5-8. The results are shown in Table 3.

Comparative Example 6
In Example 1, the reaction was performed in the same manner as in Example 1 except that the molar ratio of ethylenediamine / ethylene dichloride was changed to 2. The results are shown in Table 3.

Comparative Example 7
In Example 1, the reaction was performed in the same manner as in Example 1 except that the reaction temperature was changed to 60 ° C. The results are shown in Table 3.

Comparative Example 8
In Example 1, the reaction was performed in the same manner as in Example 1 except that a 50% by weight aqueous solution of diethylenetriamine was used instead of the 70% by weight aqueous solution of ethylenediamine and the reaction temperature was changed to 60 ° C. The results are shown in Table 3.

  Tables 1, 2 and 3 show that polyalkylene polyamine mixtures can be obtained with higher yields and higher selectivity for linear polyalkylene polyamines than conventional methods. It was.

  According to the present invention, it is possible to selectively obtain a linear polyalkylene polyamine used for an epoxy resin curing agent or the like. That is, the present invention has a possibility of being widely used in the field of producing amine derivatives.

Claims (6)

A process for producing a polyalkylene polyamine in which a raw material polyalkylene polyamine having a primary amino group is reacted with ethylene dichloride, wherein the raw material polyalkylene polyamine having a primary amino group is used in an amount of at least 4 molar equivalents relative to ethylene dichloride, at 100 ° C. A process for producing a polyalkylene polyamine mixture, wherein the reaction is carried out in a temperature range of 200 ° C. or lower. The method for producing a polyalkylene polyamine mixture according to claim 1, wherein the starting polyalkylene polyamine having a primary amino group is ethylenediamine, diethylenetriamine, dipropylenetriamine, dibutylenetriamine, or N-aminoethylpiperazine. The method for producing a polyalkylene polyamine mixture according to claim 1 or 2, wherein the starting polyalkylene polyamine having a primary amino group is ethylenediamine or diethylenetriamine. The method for producing a polyalkylene polyamine mixture according to any one of claims 1 to 3, wherein the concentration of the starting polyalkylene polyamine having a primary amino group is 30% by weight or more. The method for producing a triethylenetetramine mixture according to claim 1, wherein ethylenediamine is used in an amount of 4 molar equivalents or more with respect to ethylene dichloride, and the reaction is performed in a temperature range of 120 ° C or higher and 180 ° C or lower. 2. The method for producing a pentaethylenehexamine mixture according to claim 1, wherein diethylenetriamine is used in an amount of 8 molar equivalents or more with respect to ethylene dichloride, and the reaction is performed in a temperature range of 120 ° C. or more and 180 ° C. or less.