JP2018070472A - Manufacturing method of guanidine oxalate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method capable of producing guanidine oxalate, particularly aminoguanidine oxalate, easily and in a high yield. SOLUTION: A powder containing a carbonate (A) of a guanidine compound represented by the following general formula (1) in the presence of one or more selected from the group consisting of water and a polar organic solvent (D). A method for producing guanidine oxalate, which comprises a mixing step of mixing the granules and the powder granules containing the oxalic acid compound (B). [Chemical formula 1] (In the formula, X is a hydrogen atom, an amino group or an organic group which may have a substituent, Y is a hydrogen atom or an amino group, and Z is a hydrogen atom or a substituent. It is an amino group that may have.) [Selection diagram] None

Description

  The present invention relates to a method for producing guanidine oxalate.

  Azodicarbonamide (hereinafter also referred to as “ADCA”), which is a typical gas generating agent, is a compound used in a wide range of applications as a chemical foaming agent for plastics and rubber in general (for example, Patent Document 1 and Non-Patent Document 1). Patent Document 1).

  The excellent point of ADCA is that the amount of generated gas is as large as 200 mL / g or more compared with other commercially available chemical foaming agents, and the combination with a foaming aid having a relatively high decomposition start temperature of 200 to 210 ° C. The decomposition start temperature can be lowered to around 140 ° C, it can be applied to general-purpose plastics (for example, thermoplastic resins) and rubber, and the generated gas is mainly composed of nitrogen and self-extinguishing, so it is safe to handle. It is expensive.

  On the other hand, 4,4′-oxybis (benzenesulfonylhydrazide) (hereinafter also referred to as “OBSH”), in which the generated gas is only nitrogen and water and the decomposition products are non-polluting, is also used as a gas generating agent ( For example, see Patent Document 2). OBSH has a low decomposition initiation temperature of about 170 ° C., and is mainly used for ethylene-propylene-diene rubber (EPDM) for weather strips and chloroprene rubber (CR) for wet suits.

  In addition to ADCA and OBSH, guanidine derivatives such as guanidine salts, aminoguanidine salts, diaminoguanidine salts, and triaminoguanidine salts can also be used as gas generating agents. These guanidine derivatives are also used for explosives, pharmaceuticals, antioxidants for fiber processing, soap resin stabilizers, and various other synthetic raw materials (for example, see Non-Patent Document 2). Specifically, for example, gas generating agents containing carbonates, nitrates, and perchlorates of guanidine derivatives are disclosed for airbag systems (see, for example, Patent Documents 2 to 5).

Japanese Patent Laid-Open No. 11-21364 International Publication No. 97/29927 JP 11-292678 A Japanese Patent No. 3953187 Japanese Patent Application No. 2015-088657

Kondo Hitoshi, “Thermal Decomposable Foaming Agents and Their Characteristics”, Journal of the Japan Rubber Association, Japan Rubber Association, 2001, Vol. 74, No. 10, p. 406-411 “Guanidine salt”, Fine Chemical, CMC Publishing, June 2008, Vol. 37, No. 6, p. 72-75

  However, ADCA contains a small amount of ammonia gas in the gas generated at the time of foaming. This ammonia gas exhibits corrosiveness, and cyanic acid, which is a decomposition product of ADCA, is sublimable and polymerizes after sublimation. Therefore, it has corrosive cyanuric acid, which tends to cause mold contamination (see, for example, Patent Document 1 and Non-Patent Document 1).

  Further, OBSH has a small amount of generated gas of 120 mL / g, and it is necessary to increase the amount of addition in order to obtain a desired expansion ratio, which has a problem in terms of economy and resource saving.

  On the other hand, among the guanidine derivatives, aminoguanidine oxalate has an appropriate decomposition temperature in general-purpose plastics (for example, thermoplastic resins) and rubber foam molding, and has a larger amount of generated gas than OBSH. It can be used as a gas generating agent containing almost no corrosive gas.

  However, since guanidine oxalate such as aminoguanidine oxalate is water-soluble, the conventional aqueous solution-based synthesis method has a low molar yield of about 70%, which is inferior in economic efficiency. On the other hand, organic solvent-based synthesis methods have problems that wastewater treatment becomes difficult and the environmental load increases. Therefore, it is difficult to provide aminoguanidine oxalate inexpensively as a gas generator for general-purpose plastics and rubber, such as ADCA and OBSH, in the conventional method for producing guanidine oxalate.

  Then, an object of this invention is to provide the manufacturing method which can manufacture guanidine oxalate, especially aminoguanidine oxalate simply and with high yield.

  As a result of intensive studies on the above problems, the present inventors have mixed a granular material containing a carbonate of a guanidine compound having a predetermined structure and a granular material containing an oxalic acid compound in the presence of water or the like. It has been found that guanidine oxalate can be easily produced in a high yield by using a production method having the above, and the present invention has been completed.

That is, the present invention is as follows.
[1]
In the presence of one or more selected from the group consisting of water and a polar organic solvent (D), a granular material containing a carbonate (A) of a guanidine compound represented by the following general formula (1); Having a mixing step of mixing the oxalic acid compound (B) -containing granule,
A method for producing guanidine oxalate.
(In the formula, X is a hydrogen atom, an amino group or an organic group which may have a substituent, Y is a hydrogen atom or an amino group, and Z may have a hydrogen atom or a substituent. Good amino group.)
[2]
The method for producing guanidine oxalate according to [1], wherein the oxalic acid compound (B) is oxalic acid hydrate.
[3]
The method for producing guanidine oxalate according to [2], wherein the mixing step is a step of further mixing one or more selected from the group consisting of water (C) and a polar organic solvent (D). .
[4]
The oxalic acid compound (B) is oxalic anhydride, and the mixing step further mixes one or more selected from the group consisting of water (C) and a polar organic solvent (D). The method for producing guanidine oxalate according to [1], which is a step.
[5]
In the mixing step, the total number of moles of water and the polar organic solvent (D) is 0.5 to 3.0 moles relative to the number of moles of oxalic acid in the oxalic acid compound (B). The method for producing guanidine oxalate according to any one of [1] to [4].
[6]
The method for producing guanidine oxalate according to any one of [1] to [5], wherein the mixing step is performed by mixing at a temperature of 0 ° C. to 100 ° C. and a time of 1.0 minute to 24 hours. .
[7]
The method for producing guanidine oxalate according to any one of [1] to [6], further comprising a drying step of drying under a condition of a temperature of 0 ° C. or higher and 100 ° C. or lower after the mixing step.
[8]
The guanidine oxalate salt according to any one of [1] to [7], wherein the polar organic solvent (D) is one or more selected from the group consisting of methanol, ethanol, acetone, and dimethyl sulfoxide. Manufacturing method.
[9]
The method for producing guanidine oxalate according to any one of [1] to [8], wherein the oxalic acid compound (B) is oxalic acid dihydrate.
[10]
The molar ratio ((A) :( B)) between the carbonate (A) of the guanidine compound and the oxalic acid compound (B) is in the range of 1: 1 to 2: 1 [1] to [9 ] The manufacturing method of the guanidine oxalate in any one of.
[11]
The carbonate (A) of the guanidine compound is an aminoguanidine carbonate,
The method for producing guanidine oxalate according to any one of [1] to [10], wherein the guanidine oxalate is aminoguanidine oxalate.

  According to the method for producing guanidine oxalate of the present invention, guanidine oxalate, particularly aminoguanidine oxalate can be produced simply and with high yield.

  Hereinafter, a mode for carrying out the present invention (hereinafter also referred to as “the present embodiment”) will be described in detail. The following embodiments are examples for explaining the present invention, and are not intended to limit the present invention to the following contents. The present invention can be appropriately modified within the scope of the gist.

[Method for producing guanidine oxalate]
The method for producing guanidine oxalate of the present embodiment is in the presence of one or more selected from the group consisting of water and a polar organic solvent (D) (hereinafter also simply referred to as “water etc.”). Carbonate (A) of guanidine compound represented by the following general formula (1) (hereinafter, also simply referred to as “carbonate of guanidine compound (A)”, “carbonate of guanidine compound”, “(A)”) And a granule containing the oxalic acid compound (B) (hereinafter also simply referred to as “oxalic acid compound” or “(B)”).
(In the formula, X is a hydrogen atom, an amino group or an organic group which may have a substituent, Y is a hydrogen atom or an amino group, and Z may have a hydrogen atom or a substituent. Good amino group.)

  According to the production method of the present embodiment, guanidine oxalate can be produced simply and with high yield. More specifically, by mixing the granular material containing (A) and the granular material containing (B), a guanidine oxalate solid can be synthesized in high yield and dried in the atmosphere. Alternatively, the desired guanidine oxalate can be obtained only by the drying step described later. Further, since the water used in the mixing step is relatively small, it can be easily removed by drying by airflow drying, reduced pressure drying or the like. For this reason, compared with the method of reacting with an aqueous solution system or an organic solvent system, it is simple without requiring an operation such as removing a large amount of an aqueous solvent or an organic solvent or a washing operation.

[Mixing process]
The mixing step of this embodiment is a step of mixing a granular material containing a carbonate (A) of a guanidine compound and a granular material containing an oxalic acid compound (B) in the presence of water or the like. The means for mixing is not particularly limited as long as it can mix powder particles. Examples of such means include means for mixing using a mortar, means for mixing using a ball mill, and means for mixing using a commercially available mixer.

  Here, “powder body” means a powdery particle shape. For example, the carbonate (A) of a guanidine compound is usually solid at room temperature, and the carbonate (A) of a guanidine compound that is commercially available as a reagent generally forms a granular material. Is. Similarly, the oxalic acid compound (B) is usually solid at normal temperature, and the oxalic acid compound (B) commercially available as a reagent is generally formed into a granular material. . When these are solids that are not powder, they can be used in the form of powder by operations such as pulverization by known means.

  The particle diameter of the granular material containing the carbonate (A) of the guanidine compound is not particularly limited, but is preferably in the range of 1 μm to 500 μm, more preferably in the range of 10 μm to 100 μm. When the particle diameter is 1.0 μm or more, the handling of the powder tends to be easy, and when the particle diameter is 500 μm or less, the dispersibility of the powder is improved and the reactivity is improved. It tends to increase.

  Although the particle diameter of the granular material containing the oxalic acid compound (B) is not particularly limited, it is preferably in the range of 1.0 μm to 1000 μm, more preferably in the range of 10 μm to 500 μm. When the particle diameter is 1.0 μm or more, the handling of the powder tends to be easy, and when the particle diameter is 1000 μm or less, the dispersibility of the powder is improved and the reactivity is improved. It tends to increase.

  The water content of the granular material containing the carbonate (A) of the guanidine compound is preferably 30% by mass or less, more preferably 20% by mass or less, with respect to the total amount (100% by mass) of the granular material. More preferably 10% by mass or less, still more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less, and most preferably 1.0% by mass or less. When the water content is 30% by mass or less, the drying process after the reaction tends to be easy.

  The water content of the granular material containing the oxalic acid compound (B) is preferably 50% by mass or less, more preferably 30% by mass or less, with respect to the total amount (100% by mass) of the granular material. More preferably, it is 10 mass% or less, More preferably, it is 5.0 mass% or less, More preferably, it is 3.0 mass% or less, Most preferably, it is 1.0 mass% or less. When the water content is 50% by mass or less, the drying process after the reaction tends to be easy.

  In this embodiment, a mixing process mixes in presence of 1 type, or 2 or more types selected from the group which consists of water and a polar organic solvent (D). Here, “water” is a concept including water existing as molecules and water (C) described later. That is, “water” here is a concept that further includes crystal water and hydrated water. “Crystal water” refers to a component used in the mixing process (for example, a guanidine compound carbonate (A) or an oxalic acid compound (B)) without forming a covalent bond with a molecule or ion constituting the crystal. Means water contained in the crystal. In addition, “hydration water” means water molecules in the crystals of components used in the mixing step, in which molecules or ions constituting the crystals are attracted and bound to the periphery by hydrogen bonds or the like. Specific examples of the hydrated water include water molecules in oxalic acid hydrate described later.

  In the present embodiment, the mixing step is preferably such that the oxalic acid compound (B) is an oxalic acid hydrate because the reaction operation for obtaining guanidine oxalate can be simplified.

  In this embodiment, it is used for a mixing process that a mixing process is a process which further mixes 1 type, or 2 or more types selected from the group which consists of the water (C) and polar organic solvent (D) which are mentioned later. It is preferable because the component can be selected from other than a compound containing water of crystallization or water of hydration.

  In this embodiment, the mixing step is one or two selected from the group consisting of the oxalic acid compound (B) being oxalic anhydride and water (C) and polar organic solvent (D) described later. The step of further mixing the seeds or more is preferable because the reaction for obtaining guanidine oxalate can be easily controlled.

  The total amount (total number of moles) of water and polar organic solvent (D) used in the mixing step is 0.5 to 3.0 moles relative to the number of moles of oxalic acid in the oxalic acid compound (B). It is preferable that it is 1.0 mol or more and 2.0 mol or less. When the total number of moles is 0.5 mol or more, the reaction between the granular material containing the carbonate (A) of the guanidine compound and the granular material containing the oxalic acid compound (B) tends to proceed. . Moreover, it exists in the tendency for the drying process after reaction to become easy because a total mole number is 3.0 mol or less.

  In the present embodiment, the temperature in the mixing step is not particularly limited, but the temperature is preferably 0 ° C. or higher and 100 ° C. or lower in order to increase the yield and finish the reaction in a short time. A temperature of 50 ° C. or lower is particularly preferable from the viewpoint of increasing the purity.

  In the present embodiment, the time in the mixing step is not particularly limited, but mixing under conditions of 1.0 minute or more and 24 hours is preferable from the viewpoint of increasing the yield.

<Carbonate of guanidine compound (A)>
The carbonate (A) of the guanidine compound of this embodiment is a salt of a guanidine compound and carbonic acid. The carbonate (A) of the guanidine compound is not particularly limited as long as it is a salt of a compound represented by the following general formula (1) and carbonic acid. For example, guanidine carbonate, (bi) aminoguanidine carbonate, and (heavy) ) Diaminoguanidine carbonate. Among these, (bi) aminoguanidine carbonate is preferable from the viewpoint of more reliably obtaining the effects of the present invention. When the carbonate (A) of the guanidine compound is (bi) aminoguanidine carbonate (a carbonate of aminoguanidine), the resulting guanidine oxalate is aminoguanidine oxalate.
(In the formula, X is a hydrogen atom, an amino group or an organic group which may have a substituent, Y is a hydrogen atom or an amino group, and Z may have a hydrogen atom or a substituent. Good amino group.)

  Examples of X include a hydrogen atom, an amino group, and an organic group (for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a phenyl group, a nitro group, a cyano group, and an aminophenyl group). Moreover, as Z, a hydrogen atom and an amino group are mentioned, for example.

  The carbonate (A) of the guanidine compound mentioned above can be used alone or in combination of two or more.

<Oxalic acid compound (B)>
The oxalic acid compound (B) of the present embodiment is a compound having an oxalic acid skeleton that can take the form of a granular material. The oxalic acid compound (B) is not particularly limited, and examples thereof include oxalic acid, oxalic acid hydrate, oxalic acid anhydride, and oxalate. Examples of oxalic acid hydrate include oxalic acid dihydrate. Examples of the oxalate include sodium hydrogen oxalate.

  The oxalic acid compound (B) is preferably oxalic acid hydrate, and more preferably oxalic acid dihydrate. Since the oxalic acid compound (B) is an oxalic acid hydrate, the hydrated water in the oxalic acid hydrate functions as the above-described water and the like, so that guanidine oxalate can be produced more easily. It tends to be possible.

  The oxalic acid compound (B) is also preferably oxalic acid, oxalic anhydride, or oxalate. When the oxalic acid compound (B) is oxalic acid, oxalic anhydride, or oxalate, in the mixing step, water (C) and a polar organic solvent (D) described later are further mixed to form water. The reaction for obtaining guanidine oxalate is unlikely to proceed until (C) or the polar organic solvent (D) is mixed. Since the reaction is likely to proceed after mixing, the reaction can be easily controlled. .

  The oxalic acid compound (B) is preferably an oxalic acid compound containing no sodium atom in the compound when the obtained guanidine oxalate is used as a gas generating agent, more preferably oxalic acid dihydrate and oxalic acid anhydride. preferable. Since the oxalic acid compound (B) is an oxalic acid compound that does not contain sodium atoms in the compound, the gas generating agent does not contain sodium atoms, the moldability is improved, and contamination after molding is suppressed. It tends to be. In addition, such a gas generating agent can be suitably used as an exterior material by preventing deterioration of water resistance and moisture resistance because no sodium atom remains as sodium carbonate.

  The oxalic acid compound (B) described above can be used alone or in combination of two or more.

  In the present embodiment, the molar ratio ((A) :( B)) between the carbonate (A) of the guanidine compound and the oxalic acid compound (B) is preferably in the range of 1: 1 to 2: 1. When the molar ratio is within the above range, the obtained guanidine oxalate tends to be obtained with high purity.

<Water (C)>
Although the water (C) of this embodiment is not specifically limited, For example, distilled water, purified water, and ion exchange water are mentioned.

<Polar organic solvent (D)>
The polar organic solvent (D) of the present embodiment (hereinafter also simply referred to as “polar organic solvent”) is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, propanol, isopropyl alcohol, butanol, and isobutyl alcohol, Acetone and dimethyl sulfoxide are mentioned. Among these, 1 type, or 2 or more types selected from the group which consists of methanol, ethanol, acetone, and dimethyl sulfoxide is preferable.

  The polar organic solvent (D) can be used alone or in combination of two or more.

  The amount of water (C) and polar organic solvent (D) used may be small enough to be easily removed in the drying step described below.

  That is, the total amount of water (C) and polar organic solvent (D) used is preferably within the range of the total amount of water and polar organic solvent (D) used in the mixing step described above, and the oxalic acid compound (B ) It is preferable that it is 10 to 70 mass parts with respect to 100 mass parts. When the total amount of water (C) and polar organic solvent (D) used is 10 parts by mass or more, the reaction tends to proceed, and the total amount of water (C) and polar organic solvent (D) used. Is 70 parts by mass or less, the drying process after the reaction tends to be easy.

  As described above, when the oxalic acid compound (B) is oxalic acid hydrate, the water in the oxalic acid hydrate is not further mixed with water (C) and the polar organic solvent (D). Guanidine oxalate can be produced in the presence of Japanese water.

[Drying process]
It is preferable that the manufacturing method of the guanidine oxalate of this embodiment further has a drying process which dries guanidine oxalate after a mixing process. The means for drying in the drying step is not particularly limited, and can be performed by a known means such as airflow drying or reduced pressure drying. By having a drying process, water used in the mixing process can be easily removed.

  The drying step is preferably a step of drying under conditions where the temperature is 0 ° C. or higher and 100 ° C. or lower from the viewpoint of the stability of the product.

[Use]
The guanidine oxalate obtained by the production method of the present embodiment is suitably used for applications such as a gas generating agent, a rubber material additive, and a protein denaturant. Of these, aminoguanidine oxalate is suitably used for gas generating agents.

  Hereinafter, the present embodiment will be described more specifically with reference to examples and comparative examples. However, the present embodiment is not limited to the examples. In the following examples and comparative examples, unless otherwise limited, the compounds were identified by CHN elemental analysis and FT-IR. Moreover, the decomposition temperature of gas generating agent and the amount of generated gas were measured by the following methods, respectively.

<Measurement of decomposition temperature of gas generant>
The decomposition temperature of the gas generating agent was measured by using a melting point measuring apparatus (“B540” manufactured by Büch) under the condition of increasing the temperature at 190 ° C. in the atmosphere at 5 ° C./min. The decomposition temperature was a temperature at which a change in color tone due to decomposition was visually confirmed.

<Measurement of generated gas amount>
Take 0.5 g of gas generant in a test tube, add 10 mL of liquid paraffin as a heating medium, connect the test tube and gas burette with a rubber tube, immerse the test tube in a 190 ° C oil bath, and heat for 30 minutes. Continued. All the gas generated during the heating was collected with a gas burette, and the amount of generated gas (mL) per 1.0 g of the gas generating agent was determined.

(Example 1) Synthesis example of aminoguanidine oxalate using oxalic acid dihydrate as a raw material 40.8 g (0.300 mol) of aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.), oxalic acid dihydrate 37.8 g (0.300 mol) (made by Wako Pure Chemical Industries, Ltd.) are weighed and put into a mixer (trade name “Ninja Chopper”, importer “Shop Japan”) and mixed at high speed in the mixer for 5 minutes. did. The state after mixing was powdery. Then, it was made to dry at 40 degreeC for 18 hours, and 49.10 g (0.299 mol) of white solid was obtained. When the obtained solid was analyzed by FT-IR, it was confirmed to be aminoguanidine oxalate. Moreover, when the obtained solid was subjected to elemental analysis using a carbon, hydrogen, nitrogen simultaneous determination apparatus CHN coder MT-6 (Yanako Analytical Industrial Co., Ltd.), theoretical values C: 3, H: 8, N: 4 and O: 4, the measured values were C: 2.97, H: 7.87, N: 3.96, O: 4.07, and it was confirmed to be aminoguanidine oxalate. Moreover, about the obtained solid, decomposition | disassembly start temperature and the amount of generated gas were measured on said conditions. Table 1 shows the decomposition temperature, the amount of gas generated, and the molar yield.

(Example 2) Synthesis of aminoguanidine oxalate using oxalic anhydride as a raw material and adding a small amount of water Aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 40.8 g (0.300 mol) ), 27.0 g (0.300 mol) of oxalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) were weighed and put into a mixer (trade name “Ninja Chopper”, import sales source “Shop Japan”). After mixing for 20 seconds with a mixer so that the charged raw materials were uniform, 5.4 g (0.300 mol) of distilled water was added as a small amount of water, and high speed mixing was continued in the mixer for another 5 minutes. The state after mixing was powdery. Then, it dried at 40 degreeC for 18 hours, and obtained white solid 49.1g (0.299 mol). When the obtained solid was analyzed by FT-IR, it was confirmed to be aminoguanidine oxalate. Moreover, when the obtained solid was subjected to elemental analysis using a carbon, hydrogen, nitrogen simultaneous determination apparatus CHN coder MT-6 (Yanako Analytical Industrial Co., Ltd.), theoretical values C: 3, H: 8, N: 4, O: 4, measured values C: 2.95, H: 7.71, N: 3.97, O: 4.08, confirmed to be aminoguanidine oxalate. Moreover, about the obtained solid, decomposition | disassembly start temperature and the amount of generated gas were measured on said conditions. Table 1 shows the decomposition temperature, the amount of gas generated, and the molar yield.

(Example 3) Synthesis of aminoguanidine oxalate using oxalic anhydride as a raw material and adding a small amount of ethanol. 5.4 g of distilled water added as a small amount of water in Example 2 was added to ethanol (Wako Pure Chemical Industries, Ltd.). The raw materials were mixed in the same manner as in Example 2 except that the amount was changed to 13.8 g (0.300 mol) (manufactured by Yakuhin Co., Ltd.). The state after mixing was powdery, and finally 48.58 g of a white solid was obtained. When the obtained solid was analyzed by FT-IR, it was confirmed to be aminoguanidine oxalate. Moreover, when the obtained solid was subjected to elemental analysis using a carbon, hydrogen, nitrogen simultaneous determination apparatus CHN coder MT-6 (Yanako Analytical Industrial Co., Ltd.), theoretical values C: 3, H: 8, N: 4, O: 4, measured values C: 2.97, H: 7.87, N: 3.97, O: 4.06, confirmed to be aminoguanidine oxalate. Moreover, about the obtained solid, decomposition | disassembly start temperature and the amount of generated gas were measured on said conditions. Table 1 shows the decomposition temperature, the amount of gas generated, and the molar yield.

(Comparative Example 1) Synthesis Example of Aminoguanidine Oxalate in Aqueous Solution After adding 27.0 g (0.300 mol) of oxalic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) to a 500 mL beaker and adding 90 g of water, The mixture was stirred with a stirring blade to obtain an aqueous solution of oxalic acid. Subsequently, 40.8 g (0.300 mol) of aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little and stirred for 2.5 hours. The precipitated white solid was collected by filtration, washed with ion exchange water, and then dried at 40 ° C. for 18 hours to obtain 30.44 g (0.186 mol) of a white solid. When the obtained solid was analyzed by FT-IR, it was confirmed to be aminoguanidine oxalate. Moreover, when the obtained solid was subjected to elemental analysis using a carbon, hydrogen, nitrogen simultaneous determination apparatus CHN coder MT-6 (Yanako Analytical Industrial Co., Ltd.), theoretical values C: 3, H: 8, N: 4, O: 4, measured values C: 2.97, H: 7.87, N: 3.98, O: 4.05, confirmed to be aminoguanidine oxalate. Moreover, about the obtained solid, the decomposition temperature and the amount of generated gas were measured on said conditions. Table 1 shows the decomposition initiation temperature, the amount of generated gas, and the molar yield.

(Comparative example 2) Reaction example of oxalic anhydride and aminoguanidine carbonate without using a small amount of water and polar organic solvent Aminoguanidine carbonate (manufactured by Tokyo Chemical Industry Co., Ltd.) 20.4 g (0.150 mol) , 13.5 g (0.150 mol) of oxalic acid anhydride (manufactured by Wako Pure Chemical Industries, Ltd.) was weighed and put into a mixer (trade name “Ninja Chopper”, importer “Shop Japan”) And mixed at high speed for 5 minutes. The state after mixing was powdery. Then, it was dried at 40 ° C. for 18 hours to recover 33.19 g of a white solid. When the obtained solid was analyzed by FT-IR, it did not match aminoguanidine oxalate, and peaks of raw material oxalic acid and aminoguanidine carbonate could be confirmed, respectively, and no reaction occurred. It was confirmed. Moreover, when the obtained solid was subjected to elemental analysis using a carbon, hydrogen, nitrogen simultaneous determination apparatus CHN coder MT-6 (Yanako Analytical Industrial Co., Ltd.), theoretical values C: 3, H: 8, N: 4, O: 4, measured values C: 4.41, H: 9.27, N: 6.11, O: 4.88, not aminoguanidine oxalate, theoretical value C of raw material mixture : 4, H: 10, N: 4, and O: 7.

(Comparative Example 3) Reaction Example of Oxalic Anhydride and Aminoguanidine Carbonate Using Nonpolar Organic Solvent without Using Small Amount of Water and Polar Organic Solvent Distilled Water Added as a Small Amount of Water in Example 2 The raw materials were mixed in the same manner as in Example 2 except that 4 g was changed to 25.8 g (0.300 mol) of n-hexane (manufactured by Wako Pure Chemical Industries, Ltd.). Thereafter, drying was performed in the same manner as in Example 2 to recover 67.1 g of a white solid. When the obtained solid was analyzed by FT-IR, it did not match aminoguanidine oxalate, and peaks of raw material oxalic acid and aminoguanidine carbonate could be confirmed, respectively, and no reaction occurred. It was confirmed.

Comparative Example 4 Reaction Example of Oxalic Acid Dihydrate and Aminoguanidine Hydrochloride 1.10 g (0.01 mol) of aminoguanidine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.), oxalic acid dihydrate (Japanese 1.26 g (0.01 mol) manufactured by Koyo Pure Chemical Co., Ltd. was weighed and put into a mixer (trade name “Ninja Chopper”, import sales source “Shop Japan”), and mixed at high speed in the mixer for 5 minutes. The state after mixing was powdery. Then, it was dried at 40 ° C. for 18 hours to recover 2.13 g of a white solid. When the obtained solid was analyzed by FT-IR, it did not match aminoguanidine oxalate, and the peaks of raw material oxalic acid and aminoguanidine hydrochloride could be confirmed, respectively, and there was no reaction. It was confirmed.

  From the results in Table 1, it was found that at least the molar yield was significantly improved by the production methods of Examples 1 to 3 as compared with the conventionally known production method of Comparative Example 1. Moreover, it was found that the decomposition start temperature and the amount of generated gas are not at least inferior to those of the production method of the comparative example.

Claims (11)

In the presence of one or more selected from the group consisting of water and a polar organic solvent (D), a granular material containing a carbonate (A) of a guanidine compound represented by the following general formula (1); Having a mixing step of mixing the oxalic acid compound (B) -containing granule,
A method for producing guanidine oxalate.
(In the formula, X is a hydrogen atom, an amino group or an organic group which may have a substituent, Y is a hydrogen atom or an amino group, and Z may have a hydrogen atom or a substituent. Good amino group.)   The method for producing guanidine oxalate according to claim 1, wherein the oxalic acid compound (B) is oxalic acid hydrate.   The method for producing guanidine oxalate according to claim 2, wherein the mixing step is a step of further mixing one or more selected from the group consisting of water (C) and a polar organic solvent (D). . The oxalic acid compound (B) is oxalic anhydride, and the mixing step further mixes one or more selected from the group consisting of water (C) and a polar organic solvent (D). The manufacturing method of the guanidine oxalate of Claim 1 which is a process.   In the mixing step, the total number of moles of water and the polar organic solvent (D) is 0.5 to 3.0 moles relative to the number of moles of oxalic acid in the oxalic acid compound (B). The manufacturing method of the guanidine oxalate as described in any one of Claims 1-4.   The method for producing guanidine oxalate according to any one of claims 1 to 5, wherein the mixing step is performed under the conditions of a temperature of 0 ° C to 100 ° C and a time of 1.0 minutes to 24 hours. .   The manufacturing method of the guanidine oxalate as described in any one of Claims 1-6 which further has a drying process which drys on the conditions whose temperature is 0 degreeC or more and 100 degrees C or less after the said mixing process.   The guanidine oxalate according to any one of claims 1 to 7, wherein the polar organic solvent (D) is one or more selected from the group consisting of methanol, ethanol, acetone, and dimethyl sulfoxide. Manufacturing method.   The method for producing guanidine oxalate according to any one of claims 1 to 8, wherein the oxalic acid compound (B) is oxalic acid dihydrate.   The molar ratio ((A) :( B)) of the carbonate (A) of the guanidine compound and the oxalic acid compound (B) is in the range of 1: 1 to 2: 1. The manufacturing method of the guanidine oxalate as described in any one. The carbonate (A) of the guanidine compound is an aminoguanidine carbonate,
The method for producing guanidine oxalate according to any one of claims 1 to 10, wherein the guanidine oxalate is aminoguanidine oxalate.