Alkylamine composition and method for storing alkylamine composition

Abstract

To provide an alkylamine composition and a method for storing the alkylamine composition.SOLUTION: The alkylamine composition contains 99.5% by volume or more of an alkylamine represented by the following formula (1) and 10 ppm by mass or more and 100 ppm by mass or less of water. (In the formula, N represents a nitrogen atom; R1 represents a C1 to 10 hydrocarbon group which may have a ring, a hetero atom, or a halogen atom; R2 and R3 each independently represent H or a C1 to 10 hydrocarbon group which may have a ring, a hetero atom, or a halogen atom; However, when the number of carbon atoms is 3 or more, the hydrocarbon group may have a branched-chain structure or a cyclic structure. The hetero atom of the hydrocarbon group is a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. In addition, R1 has one or more hydrogen atoms at an α - position carbon atom. ) SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to alkylamine compositions and methods for preserving the alkylamine compositions. [Background technology]

[0002] Alkylamines such as n-butylamine are used in pharmaceutical and semiconductor device manufacturing processes. It is desirable for the raw materials used in these processes to have as high a purity as possible.

[0003] On the other hand, alkylamines often cause discoloration and a decrease in purity during storage. As a method for preventing discoloration during storage, Patent Document 1 discloses a method for stabilizing aromatic amines by adding hydrazine or the like to prevent discoloration. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 3-287566 Summary of the Invention [Problem to be solved by the invention]

[0005] However, in the method described in Patent Document 1, an additive comprising hydrazine is added to the compound to be preserved. Therefore, when the amine composition containing the additive itself or a substance derived from the additive is used in the manufacturing process of a pharmaceutical product or the like, there is a possibility that a product not meeting the required properties may be manufactured.

[0006] In view of the above problems, the present disclosure aims to provide an alkylamine composition that contains small amounts of components that are unlikely to cause problems in the manufacturing process of pharmaceuticals and the like, has excellent storage stability, and is less likely to contain impurities even after long-term storage, and a method for stably storing the alkylamine composition. [Means for solving the problem]

[0007] As a result of extensive investigations, the present inventors have found that the generation of imines during long-term storage of alkylamines is the cause of a decrease in purity, and that when alkylamines contain a trace amount of water, the decrease in purity due to the generation of imines during long-term storage can be suppressed and the total amount of impurities including water can also be reduced, leading to the completion of the present disclosure.

[0008] That is, the alkylamine composition of the present disclosure is characterized by containing 99.5% by volume or more of an alkylamine represented by the following general formula (1) and containing water in an amount of 10 ppm by mass or more and 100 ppm by mass or less. [ka] (In general formula (1), N is a nitrogen atom. R 1 R is a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a hetero atom or a halogen atom. 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a heteroatom, or a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, it may have a branched or cyclic structure. The heteroatom of the hydrocarbon group is a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Furthermore, R 1 and R 2 When both are hydrocarbon groups having one or more carbon atoms, R 1 and R 2 may be directly bonded to form a cyclic structure. 1 or R 2 When the double bond directly bonds to form a ring structure, R 3 may be absent to form an aromatic ring. 1 , R 2 and R 3 may be the same hydrocarbon group or different hydrocarbon groups. 1 has one or more hydrogen atoms on the carbon atom α-bonded to the nitrogen atom.

[0009] According to the alkylamine composition of the present disclosure, the alkylamine composition contains water in an amount of 10 ppm by mass or more and 100 ppm by mass or less, thereby suppressing the generation of imine impurities over a long period of time. Furthermore, although the alkylamine composition contains water in an amount of 10 ppm by mass or more and 100 ppm by mass or less, even when the alkylamine composition is used in the manufacturing process of pharmaceuticals, etc., there is little possibility that even trace amounts of water will result in the production of a product that does not meet the required properties. Meanwhile, the inclusion of water can suppress the generation of imine, which may result in the production of a product that does not meet the required properties. Furthermore, even if water is considered a potentially problematic impurity, the total amount of impurities, including water, is reduced, making the composition suitable for use in pharmaceuticals, etc.

[0010] If the alkylamine composition contains less than 10 ppm by mass of water, it becomes difficult to suppress the production of imine, and the imine content increases, which may affect the product properties when used in the manufacturing process of pharmaceuticals, etc. On the other hand, if the alkylamine composition contains more than 100 ppm by mass of water, the imine content can be reduced, but the water itself may affect the product properties when used as a raw material in manufacturing pharmaceuticals, etc.

[0011] In the alkylamine compositions of the present disclosure, the alkylamine is desirably n-butylamine. In the alkylamine composition, when the alkylamine is n-butylamine, it can be used as a raw material for manufacturing pharmaceuticals or as an optimum compound for manufacturing semiconductor devices.

[0012] The alkylamine composition of the present disclosure may further contain oxygen in an amount of 1 ppm by volume or more and 1000 ppm by volume or less. The alkylamine composition of the present disclosure further contains water within the above range even when it contains oxygen in an amount of 1 ppm by volume or more and 1000 ppm by volume or less, and therefore can suppress the production of imines for a long period of time.

[0013] In the alkylamine composition of the present disclosure, it is difficult to reduce the oxygen content to less than 1 ppm by volume. On the other hand, if the oxygen content exceeds 1000 ppm by volume, even if the water content is within the above range, the imine content will be high, and when the composition is used as a raw material in producing pharmaceuticals, etc., the imine itself may affect the product properties.

[0014] The alkylamine composition of the present disclosure preferably contains the above alkylamine in an amount of 99.9% by volume or more. When the alkylamine composition of the present disclosure contains the alkylamine at 99.9% by volume or more, the purity of the alkylamine is high and the impurity content can be reduced over a long period of time, making it more suitable for use as a pharmaceutical or the like.

[0015] The method for storing an alkylamine composition of the present disclosure is characterized by comprising a filling step of filling a container with the alkylamine composition, and a storage step of storing the container filled with the alkylamine composition at a temperature of 10°C or higher and 45°C or lower.

[0016] The method for storing an alkylamine composition according to the present disclosure includes a filling step of filling a container with the alkylamine composition, and a storage step of storing the container filled with the alkylamine composition at a temperature of 10°C or higher and 45°C or lower. Since the alkylamine composition according to the present disclosure is used as the alkylamine composition and the temperature of the container during storage is also 10°C or higher and 45°C or lower, imine production can be suppressed for a long period of time.

[0017] In the method for storing an alkylamine composition of the present disclosure, storing a container filled with the alkylamine composition at a temperature below 10° C. is undesirable because it increases the cost of cooling. On the other hand, storing a container filled with the alkylamine composition at a temperature above 45° C. is undesirable because it is prone to imine formation.

[0018] According to the storage method of the alkylamine composition of the present disclosure, even when the composition is stored at 25°C for one month, the increase in the amount of imine compounds can be kept to 100 ppm by volume or less, and the generation of imine can be suppressed even during long-term storage.

[0019] In the method for storing an alkylamine composition of the present disclosure, the container is desirably made of stainless steel (SUS), manganese steel, nickel steel, or chrome molybdenum steel. In the method for storing an alkylamine composition according to the present disclosure, if the container is made of stainless steel (SUS), manganese steel, nickel steel, or chromium-molybdenum steel, the container has sufficient mechanical strength, allowing for safe storage, and impurities are hardly eluted from the container, so that even if the alkylamine composition is stored for a long period of time, an increase in impurities such as imines can be suppressed. [Effects of the Invention]

[0020] According to the alkylamine composition of the present disclosure, although the alkylamine composition contains a very small amount of water, there is little possibility that a product not meeting the required properties will be produced due to a small amount of water, and it is possible to suppress the production of imines that may result in the production of products not meeting the required properties when used over a long period of time in the manufacturing process of pharmaceuticals, etc. Furthermore, even if water is considered to be a potentially problematic impurity, the total amount of impurities including water is also small, making the alkylamine composition suitable for use in pharmaceuticals, etc. DETAILED DESCRIPTION OF THE INVENTION

[0021] The present disclosure will be described in detail below, but the following description of the constituent elements is an example of an embodiment of the present disclosure, and the present disclosure is not limited to these specific details. Various modifications can be made within the scope of the gist of the present disclosure.

[0022] The alkylamine composition of the present disclosure is characterized by containing 99.5% by volume or more of an alkylamine represented by the following general formula (1) and containing water in an amount of 10 ppm by mass or more and 100 ppm by mass or less. [ka] (In general formula (1), N is a nitrogen atom. R 1 R is a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a hetero atom or a halogen atom. 2 and R 3 are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a heteroatom, or a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, it may have a branched or cyclic structure. The heteroatom of the hydrocarbon group is a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. Furthermore, R 1 and R 2 When both are hydrocarbon groups having one or more carbon atoms, R 1 and R 2 may be directly bonded to form a cyclic structure. 1 or R 2 When the double bond directly bonds to form a ring structure, R 3 may be absent to form an aromatic ring. 1 , R 2 and R 3 may be the same hydrocarbon group or different hydrocarbon groups. 1 has one or more hydrogen atoms on the carbon atom α-bonded to the nitrogen atom.

[0023] According to the alkylamine composition of the present disclosure, the alkylamine composition contains water in an amount of 10 ppm by mass or more and 100 ppm by mass or less, thereby suppressing the generation of imine impurities over a long period of time. Furthermore, although the alkylamine composition contains water in an amount of 10 ppm by mass or more and 100 ppm by mass or less, even when the alkylamine composition is used in the manufacturing process of pharmaceuticals, etc., there is little possibility that even trace amounts of water will result in the production of a product that does not meet the required properties. Meanwhile, the inclusion of water can suppress the generation of imine, which may result in the production of a product that does not meet the required properties. Furthermore, even if water is considered a potentially problematic impurity, the total amount of impurities, including water, is reduced, making the composition suitable for use in pharmaceuticals, etc.

[0024] In the alkylamine represented by the general formula (1), examples of the halogen atom that may be contained in the hydrocarbon group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Furthermore, when the hydrocarbon group has three or more carbon atoms, the hydrocarbon group may be a branched hydrocarbon group such as an isopropyl group, an aromatic hydrocarbon group such as a phenyl group, or an alicyclic hydrocarbon group that does not contain a non-aromatic conjugated double bond, such as a cyclohexyl group. The alkylamine represented by the general formula (1) may be a heterocyclic amine having a five-membered ring structure or a six-membered ring structure.

[0025] Examples of the alkylamine include tertiary amines such as trimethylamine, triethylamine, dimethylethylamine, and diethylmethylamine. Examples of the alkylamine include secondary amines such as dimethylamine, diethylamine, di-n-propylamine, diisopropylamine, dibutylamine, N-methylethylamine, N-methylpropylamine, N-methylbutylamine, and N-methylpentylamine. Examples of the alkylamine include heterocyclic amines such as pyrrolidine, piperidine, piperazine, pyridine, and pyrazine. Examples of the alkylamine include primary amines such as methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, n-pentylamine, n-hexylamine, and n-heptylamine.

[0026] In the above general formula (1), R 2 and R 3 is preferably a hydrogen atom. 1 is preferably a hydrocarbon group having no heteroatoms and no halogen atoms. In addition, in the general formula (1), R 1 is a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 7 carbon atoms, and more preferably a hydrocarbon group having 3 to 6 carbon atoms. Therefore, the alkylamine is preferably n-propylamine, isopropylamine, n-butylamine, sec-butylamine or isobutylamine, and particularly preferably n-butylamine.

[0027] When the alkylamine composition is an n-butylamine composition, the content of alkylamines other than n-butylamine, such as isobutylamine, is preferably 0.05% by volume or less. If the content of alkylamines other than n-butylamine is high, there is a risk that products that do not meet the required properties may be produced in the manufacturing process of pharmaceuticals, etc.

[0028] The alkylamine composition of the present disclosure is a high-purity alkylamine composition containing 99.5% by volume or more of the alkylamine represented by the general formula (1), preferably 99.9% by volume or more, and particularly preferably 99.95% by volume or more of the alkylamine. The higher the purity of the alkylamine composition, the more suitable it can be used in pharmaceutical manufacturing processes and semiconductor device manufacturing processes.

[0029] The alkylamine composition of the present disclosure contains water in an amount of 10 ppm by mass or more and 100 ppm by mass or less, and preferably 30 ppm by mass or more and 80 ppm by mass or less. This is because imine formation can be further suppressed. Alkylamines purified by distillation or the like may contain water in an amount of less than 10 ppm. In such cases, the water content is adjusted by adding water such as ultrapure water. In this case, it is desirable to remove dissolved oxygen from the water to be added in advance by nitrogen bubbling or the like.

[0030] The alkylamine composition of the present disclosure may contain oxygen in an amount of 1 ppm by volume or more and 1000 ppm by volume or less, or may contain oxygen in an amount of 10 ppm by volume or more and 100 ppm by volume or less. Alkylamines are prone to producing imines during long-term storage, but water is also produced at the same time. The imines produced during storage of alkylamine compositions are compounds having a carbon-nitrogen double bond (C=N), and water (HO) is also produced at the same time. Therefore, it is presumed that the imines are produced by a reaction between the oxygen contained in the alkylamine composition and the amine. Therefore, it is thought that the less oxygen there is in the alkylamine composition, the less likely it is that imines will be produced, but it is not easy to reduce the oxygen content to less than 1 ppm by volume. Furthermore, even if the alkylamine composition contains oxygen at a rate of 1,000 ppm by volume or less, the production of imines can be reliably suppressed by reducing the water content in the alkylamine composition to 10 ppm by mass or more and 100 ppm by mass or less.

[0031] The alkylamine composition may contain impurities other than alkylamine, moisture, and oxygen. Examples of such impurities include inert gases and nitrogen. The content of these impurities is preferably 20 ppm by volume or less.

[0032] Next, a method for storing the alkylamine composition will be described. The method for storing an alkylamine composition of the present disclosure is characterized by comprising a filling step of filling a container with the alkylamine composition of the present disclosure, and a storage step of storing the container filled with the alkylamine composition at a temperature of 10°C or higher and 45°C or lower.

[0033] In the method for preserving an alkylamine composition of the present disclosure, the filling step involves filling the alkylamine composition into a container. In this case, it is desirable to fill the composition in a liquid state. Since most of the alkylamine compositions of the present disclosure are liquid at the above temperature, they can be filled into a storage container in a liquid state. Even if the alkylamine composition of the present disclosure is a gas at room temperature, it can be liquefied by filling it under pressure. In this case, since the vapor pressure is not very high, it can be safely filled into a metal container such as a gas cylinder using a pump or the like.

[0034] The container into which the alkylamine composition is filled is not particularly limited, and examples thereof include containers made of stainless steel (SUS), manganese steel, nickel steel, and chromium molybdenum steel.

[0035] After filling the alkylamine composition into a container, the container filled with the alkylamine composition is stored at a temperature of 10°C or higher and 45°C or lower.

[0036] Setting the storage temperature below 10°C is undesirable because it requires the storage container to be cooled to below 10°C, which increases the storage cost. On the other hand, setting the storage temperature above 45°C is undesirable because it requires heating, which increases the heating cost and also makes it easier for imine to be produced.

[0037] In the storage step, there is no problem if the container filled with the alkylamine composition is stored in a storage cabinet capable of storage at a temperature near room temperature, but it is preferable to store it in a storage cabinet capable of storage at a constant temperature of around 25°C.

[0038] In the alkylamine composition of the present disclosure, the increase in the amount of imine compounds can be kept to 100 ppm by volume or less even when stored for one month at 25° C. Therefore, according to the method for storing an alkylamine composition of the present disclosure, imine formation can be sufficiently suppressed even during long-term storage.

[0039] When the alkylamine composition is stored at 25° C. for one month, the increase in the amount of the imine compound is preferably 80 ppm by volume or less, and more preferably 30 ppm by volume or less.

[0040] When actually using an alkylamine composition after storing the container filled with the alkylamine composition for a predetermined period of time, the container in which the alkylamine composition is stored is transported to the site, and the container is heated to the boiling point of the alkylamine composition or a temperature close to the boiling point to vaporize the alkylamine composition into a gaseous composition, which can be supplied to a target device via piping, etc. Alternatively, after storing the alkylamine composition of the present disclosure, the alkylamine composition can be taken out as a liquid and supplied to a target device via piping, etc. If the storage location and the production equipment, etc. are close to each other, the storage container and the production equipment, etc. can be connected by piping so that the alkylamine composition of the present disclosure can be supplied to the production equipment, etc. as needed.

[0041] Examples of the means for heating the container include a method of covering the container with a mantle heater, and a method of covering the container with a jacket through which a heat transfer medium such as hot water or steam flows. The flow rate of the gas composition varies depending on the configuration of the given device and is not particularly limited, but the flow rate of the gas composition can be controlled, for example, by a mass flow controller or the like. [Example]

[0042] Examples that more specifically disclose embodiments of the present disclosure are given below, but the present disclosure is not limited to these examples.

[0043] [Example 1] A raw material containing n-butylamine was distilled to obtain an n-butylamine composition with a purity of 99.99% by volume and a water content of 8 ppm by mass. The oxygen concentration was estimated to be between 1 ppm and 1000 ppm by volume. The oxygen concentration was calculated from the imine compound content by liquid-phase analysis using a gas chromatograph analyzer (GC-2030, manufactured by Shimadzu Corporation, detector: FID). Specifically, the oxygen concentration can be calculated from the estimated mechanism in which 1 mol of imine compound is produced from 2 mol of butylamine and 1 mol of O2.

[0044] Ultrapure water was then added to prepare an n-butylamine composition with a water content of 50 ppm by mass. Note that, since the amount of dissolved oxygen in the ultrapure water is negligibly small, the oxygen concentration of the n-butylamine composition in each example is approximately the same.

[0045] The n-butylamine composition obtained by the above preparation was filled in an amount of 0.9 L into a 1 L stainless steel container at room temperature and stored at 25°C. Thereafter, the n-butylamine composition inside was sampled every month, and the purity of n-butylamine and the content of the imine compound (N-butylbutanimine) were measured by gas chromatography using a gas chromatograph analyzer (GC-2030, manufactured by Shimadzu Corporation, detector: FID). The water content was measured using a Karl Fischer moisture meter (instrument: MKC-610, manufactured by Kyoto Electronics Co., Ltd.). The results are shown in Table 1.

[0046] [Table 1]

[0047] [Example 2] The n-butylamine composition prepared in the same manner as in Example 1, except that ultrapure water was added to prepare an n-butylamine composition with a water content of 90 ppm by mass, was filled into a container at room temperature and stored at 25°C. Then, every month, the purity of n-butylamine and the content of the imine compound (N-butylbutanimine) in the n-butylamine composition were measured by gas chromatography, and the water content was measured using a Karl Fischer moisture meter. The results are shown in Table 2.

[0048] [Table 2]

[0049] [Comparative Example 1] A raw material containing n-butylamine was distilled in the same manner as in Example 1 to obtain n-butylamine with a purity of 99.99% by volume and a water content of 8 ppm by mass. Then, 0.9 L of the n-butylamine composition obtained in the same manner as in Example 1 was filled into a 1 L SUS container and stored at 25°C, except that no ultrapure water was added.

[0050] Thereafter, the purity of n-butylamine and the content of the imine compound (N-butylbutanimine) in the n-butylamine composition were measured every month by gas chromatography, and the water content was measured using a Karl Fischer moisture meter. The results are shown in Table 3.

[0051] [Table 3]

[0052] As is clear from the results shown in Tables 1 to 3, in Comparative Example 1, where the water content was less than 10 ppm by mass, the amount of imine compounds increased significantly over time, accompanied by a slight increase in water content, whereas in Examples 1 and 2, where the water content was 10 ppm by mass or more, the amount of imine compounds did not increase as significantly. Considering the total amount of water and imine compounds as the amount of impurities, intentionally adding water suppresses the production of imine compounds, and therefore Examples 1 and 2 resulted in lower impurity concentrations than Comparative Example 1.

[0053] This application claims priority under the Paris Convention or the laws of countries transitioning to the Paris Convention, based on Japanese Patent Application No. 2020-115757 filed on July 3, 2020. The contents of that application are incorporated herein by reference in their entirety.

Claims

[Claim 1] An alkylamine composition comprising 99.5% by volume or more of an alkylamine represented by the following general formula (1) and containing 10 ppm by mass or more and 100 ppm by mass or less of water: 【Chemistry 1】 (In general formula (1), N is a nitrogen atom. R １ R is a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a hetero atom, or a halogen atom. ２ and R ３ are each independently a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms which may have a ring, a hetero atom or a halogen atom. However, when the hydrocarbon group has 3 or more carbon atoms, it may have a branched or cyclic structure. The hetero atom of the hydrocarbon group is a nitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom. Furthermore, R １ and R ２ When both are hydrocarbon groups having one or more carbon atoms, R １ and R ２ may be directly bonded to form a cyclic structure. １ or R ２ When R is directly bonded to R via a double bond to form a cyclic structure, ３ may be absent to form an aromatic ring. １ , R ２ and R ３ may be the same hydrocarbon group or different hydrocarbon groups. １ has one or more hydrogen atoms on the carbon atom α-bonded to the nitrogen atom.)

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