JP6421100B2 - Method for producing carboxamide compound - Google Patents

Description

  The present invention relates to a method for producing a carboxylic acid amide compound having an effect of thickening and stabilizing a fluid organic substance such as oil.

  The method of thickening and stabilizing the liquid is a very important technology in the industry. For example, a metastable emulsion of mayonnaise or salad dressing can stably maintain the emulsion for a long period of time. This is because the aqueous component is thickened and stabilized. For this reason, various thickening stabilizers have been developed.

  As a compound for thickening and stabilizing an aqueous medium, for example, an alkyl acrylate copolymer is known.

  On the other hand, 12-hydroxystearic acid is known as a thickening stabilizer for fluid organic substances (for example, organic substances having fluidity such as oily media) (Patent Document 1, etc.). 12-Hydroxystearic acid is mainly used for its gelling action for disposal of edible oil. However, 12-hydroxystearic acid was unable to adjust the degree of gelation and could only be induced to either solidify or remain liquid. That is, the present condition is that the compound which thickens or gelatinizes a fluid organic substance to a desired viscosity has not been found yet.

Japanese Patent Laid-Open No. 01-163111

The present inventors formed amic acid by reacting amine with benzenetetracarboxylic dianhydride, and obtained carboxylic acid amide obtained by further reacting amine in the presence of a condensing agent. It has been found that the compounds can thicken, gel or stabilize the flowable organic material to the desired viscosity (specifically, uniformly stabilize the composition containing the flowable organic material).
However, since the carboxylic acid amide compound aggregates to form a lump as soon as it is formed, it becomes difficult to stir the reaction solution as the reaction proceeds, and the composition of the reaction solution becomes non-uniform. It turned out that the purity of a thing falls and it becomes difficult to obtain the carboxylic acid amide which has a favorable thickening stabilization effect. Moreover, when producing industrially, it is very difficult to discharge | emit the reaction product used as the lump from a reaction kettle.

  Therefore, an object of the present invention is to provide a method for industrially and efficiently producing a carboxylic acid amide compound having an excellent thickening and stabilizing effect.

  As a result of intensive studies to solve the above problems, the present inventors have conducted reaction between amic acid and amine in the presence of a surfactant. Suppressed, the reaction solution can be continuously stirred until the end of the reaction, and the reaction can be carried out with the composition of the reaction solution being uniform until the end, so the molecular weight distribution is narrow and the purity is excellent and the thickening stabilization effect is excellent. The ability to produce a carboxylic acid amide compound, and because the reaction product exists in a dispersed state without forming a lump, when industrially producing, the discharge from the reaction kettle can be performed smoothly. It was possible and found to be excellent in workability. The present invention has been completed based on these findings.

（式中、Ｒ¹は前記に同じ）
で表されるアミック酸を得、得られたアミック酸に、縮合剤及び界面活性剤の存在下で、下記式（３）
Ｒ²−ＮＨ₂ （３）
（式中、Ｒ²は炭素数６以上の脂肪族炭化水素基を示す）
で表されるアミンを反応させて、下記式（４）

（式中、Ｒ¹、Ｒ²は前記に同じ。Ｒ¹とＲ²は、同一であってもよく、異なっていてもよい）
で表されるカルボン酸アミド化合物を得るカルボン酸アミド化合物の製造方法を提供する。 That is, the present invention relates to benzenetetracarboxylic dianhydride represented by the following formula (1):
R ¹ —NH ₂ (1)
(Wherein R ¹ represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (2):

(Wherein R ¹ is the same as above)
In the presence of a condensing agent and a surfactant, the following formula (3) is obtained.
R ² —NH ₂ (3)
(Wherein R ² represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (4):

(In the formula, R ¹ and R ² are the same as above. R ¹ and R ² may be the same or different.)
A method for producing a carboxylic acid amide compound is obtained.

  The present invention also provides a method for producing the above carboxylic acid amide compound, wherein the concentration of the surfactant in the reaction system is 0.001 to 1.0% by weight.

  The present invention also provides a method for producing the above carboxylic acid amide compound, wherein the condensing agent is carbodiimide.

According to the production method of the present invention, it is possible to industrially efficiently produce a carboxylic acid amide compound having a narrow molecular weight distribution and a high purity and excellent in thickening and stabilizing effect.
In addition, the carboxylic acid amide compound obtained by the production method of the present invention can easily thicken, gel, or stabilize the fluid organic substance by being compatible with the fluid organic substance. Therefore, by using them in cosmetics, paints, foods, pharmaceuticals, etc., their viscosity can be adjusted to the desired range, their composition can be kept uniform, and their usability is improved. Can do.

（式中、Ｒ¹は前記に同じ）
で表されるアミック酸を得る工程１、
及び、得られたアミック酸に、縮合剤及び界面活性剤の存在下で、下記式（３）
Ｒ²−ＮＨ₂ （３）
（式中、Ｒ²は炭素数６以上の脂肪族炭化水素基を示す）
で表されるアミンを反応させて、下記式（４）

（式中、Ｒ¹、Ｒ²は前記に同じ。Ｒ¹とＲ²は、同一であってもよく、異なっていてもよい）
で表されるカルボン酸アミド化合物を得る工程２を含む。 [Method for producing carboxylic acid amide compound]
In the method for producing a carboxylic acid amide compound of the present invention, the following formula (1)
R ¹ —NH ₂ (1)
(Wherein R ¹ represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (2):

(Wherein R ¹ is the same as above)
Step 1 for obtaining an amic acid represented by:
In the presence of a condensing agent and a surfactant, the following formula (3) is added to the obtained amic acid.
R ² —NH ₂ (3)
(Wherein R ² represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (4):

(In the formula, R ¹ and R ² are the same as above. R ¹ and R ² may be the same or different.)
The process 2 which obtains the carboxylic acid amide compound represented by these is included.

  As the benzenetetracarboxylic dianhydride, 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride can be preferably used.

R ¹ is an aliphatic hydrocarbon group having 6 or more carbon atoms, for example, about 6 to 20 carbon atoms such as hexyl, octyl, 2-ethylhexyl, decyl, lauryl, myristyl, stearyl, or nonadecyl group (preferably 6 to 6 carbon atoms). 18 and particularly preferably 8-18) linear or branched alkyl group; 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 7-octenyl, 9-decenyl, 11-dodecenyl, oleyl group Straight chain or branched alkenyl groups having about 6 to 20 carbon atoms (preferably 6 to 18 and particularly preferably 12 to 18 carbon atoms), such as hexynyl, octynyl, decynyl, pentadecynyl, octadecynyl groups and the like. A linear or branched alkynyl group having a degree (preferably 6 to 18, particularly preferably 12 to 18) can be exemplified.

  Specific examples of the amine represented by the formula (1) (hereinafter sometimes referred to as “amine (1)”) include hexylamine, octylamine, 2-ethylhexylamine, decylamine, laurylamine, and myristylamine. , Stearylamine, oleylamine and the like.

  The amount of amine (1) used (the total amount when two or more are used) is, for example, about 2 to 4 mol, preferably 2 to 3 mol, per 1 mol of benzenetetracarboxylic dianhydride.

  The reaction of benzenetetracarboxylic dianhydride and amine (1) is preferably performed in the presence of a solvent. As the solvent, for example, a proton-accepting solvent such as pyridine, triethylamine, tributylamine is preferably used. These can be used individually by 1 type or in mixture of 2 or more types.

  The amount of the solvent used is, for example, about 3 to 10 times by weight, preferably 4 to 6 times by weight, based on the total amount of benzenetetracarboxylic dianhydride and amine (1). When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

  The reaction of step 1 is usually performed under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature (or aging temperature) is, for example, about 30 to 70 ° C. The reaction time (or aging time) is, for example, about 0.5 to 5 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  The reaction solution obtained through step 1 is subjected to at least one separation means selected from, for example, filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, and the like. The amic acid separated and purified from the inside may be subjected to Step 2, or the reaction solution may be directly subjected to Step 2.

  The amic acid obtained through the step 1 is subsequently subjected to a step 2 in which an amine represented by the formula (3) (hereinafter sometimes referred to as “amine (2)”) is reacted. In the present invention, the reaction in step 2 is performed in the presence of a condensing agent and a surfactant.

R ² is an aliphatic hydrocarbon group having 6 or more carbon atoms, and examples similar to R ¹ can be given. Moreover, as amine (2), the same example as amine (1) can be given. Amine (2) may be the same as or different from amine (1). When an amine different from amine (1) is used as amine (2), a carboxylic acid amide compound in which R of the four [—CONHR] groups is two different groups is obtained. On the other hand, when the same amine as the amine (1) is used as the amine (2), a carboxylic acid amide compound in which Rs of the four [—CONHR] groups are all the same group is obtained.

  The usage-amount of amine (2) (when using 2 or more types, the total amount) is about 2-4 mol with respect to 1 mol of amic acid, Preferably it is 2-3 mol.

Examples of the condensing agent include carbodiimides represented by the following formula.
RN = C = NR ′
In the above formula, as R and R ′, for example, a linear or branched alkyl group having 3 to 8 carbon atoms which may have a heteroatom-containing substituent, or 3 to 8 membered cyclo It is an alkyl group. R and R ′ may be the same or different. R and R ′ may be bonded to each other to form a ring together with a (—N═C═N—) group.

  Examples of the linear or branched alkyl group having 3 to 8 carbon atoms include propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, isopentyl, s-pentyl, t-pentyl, Examples include hexyl, isohexyl, s-hexyl, and t-hexyl groups.

  Examples of the 3- to 8-membered cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups.

Examples of the heteroatom-containing substituent include nitrogen atom-containing substituents such as di (C _1-3 ) alkylamino groups such as amino groups and dimethylamino groups.

  Examples of the carbodiimide include diisopropylcarbodiimide, dicyclohexylcarbodiimide, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide and the like. Examples of the carbodiimide salt include hydrochloride (specifically, N- (3-dimethylaminopropyl) -N′-ethylcarbodiimide hydrochloride) and the like. These can be used alone or in combination of two or more.

  As a usage-amount of a condensing agent, it is about 2-6 mol with respect to 1 mol of amic acid, Preferably it is 2-4 mol.

  The surfactant includes a cationic surfactant, an anionic surfactant, an amphoteric surfactant, and a nonionic surfactant. These can be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a nonionic surfactant from the viewpoint of safety.

  Nonionic surfactants include ester-type nonionic surfactants, ether-type nonionic surfactants, ether-ester-type nonionic surfactants, and nitrogen-containing nonionic surfactants. Is included.

  Examples of the ester type nonionic surfactant include glycerin fatty acid esters such as diglycerin monostearate; polyoxyethylene (5) hydrogenated castor oil, polyoxyethylene (7) hydrogenated castor oil, polyoxyethylene (10 ) Hydrogenated castor oil, polyoxyethylene (20) hydrogenated castor oil, polyoxyethylene (30) hydrogenated castor oil, polyoxyethylene (40) hydrogenated castor oil, polyoxyethylene (50) hydrogenated castor oil, polyoxyethylene (60 ) Hydrogenated castor oil, polyoxyethylene hydrogenated castor oil such as polyoxyethylene (100) hydrogenated castor oil; polyoxyethylene (3) glyceryl monoisostearate, polyoxyethylene (6) glyceryl monoisostearate, polyoxyethylene (8) Glyceryl monoisostearate , Polyoxyethylene (10) glyceryl monoisostearate, polyoxyethylene (15) glyceryl monoisostearate, polyoxyethylene (20) glyceryl monoisostearate, polyoxyethylene (30) glyceryl monoisostearate, poly Polyoxy such as oxyethylene (10) glyceryl triisostearate, polyoxyethylene (20) glyceryl triisostearate, polyoxyethylene (30) glyceryl triisostearate, polyoxyethylene (40) glyceryl triisostearate Ethylene glycerin fatty acid ester; sorbitan fatty acid ester such as sorbitan monooleate, sorbitan monostearate; polyoxyethylene (6) sorbitan monolaurate, polyoxyethylene ( 0) polyoxyethylene sorbitan fatty acid esters such as sorbitan monolaurate, polyoxyethylene (20) sorbitan monostearate, polyoxyethylene (20) sorbitan monooleate; polyoxyethylene (8) trimethylolpropane trimyristate, Polyoxyethylene (20) trimethylolpropane trimyristate, polyoxyethylene (30) trimethylolpropane trimyristate, and other polyoxyethylene trimethylolpropane fatty acid esters; polyoxyethylene (30) sorbitol tetraoleate, polyoxyethylene (40) Polyoxyethylene sorbitol fatty acid esters such as sorbitol tetraoleate; polyoxyethylene (6) diisostearate, polyoxyethylene (12) Examples thereof include polyoxyethylene fatty acid esters such as diisostearate.

Examples of the ether type nonionic surfactant include the following formula (5):
R ″-[O— (AO) _n —H] _t (5)
(In the formula, R ″ represents a group obtained by removing t OH groups from the structural formula of a t-valent alcohol (t-valent organic group), and n A's are the same or different and represent an ethylene group or a propylene group. N and t are the same or different and each represents an integer of 1 or more)
The compound represented by these can be mentioned.

  Examples of the t-valent organic group include a t-valent aliphatic hydrocarbon group, a t-valent alicyclic hydrocarbon group, a t-valent aromatic hydrocarbon group, and a t-valent group obtained by combining these groups. Mention may be made of t-valent hydrocarbon groups.

The t-valent aliphatic hydrocarbon group is a group obtained by removing t hydrogen atoms from the structural formula of the aliphatic hydrocarbon. For example, the monovalent aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms (= C _1-20 ), such as a butyl group, a 2-ethylhexyl group, a lauryl group, a tridecyl group, An alkyl group having about 1 to 25 carbon atoms (preferably 5 to 23, particularly preferably 8 to 20), such as a myristyl group, a cetyl group, a stearyl group, an isostearyl group, an octyldodecyl group, a behenyl group, and a decyltetradecyl group; Examples thereof include an alkenyl group having about 2 to 20 carbon atoms (preferably 10 to 20, particularly preferably 15 to 20) such as an oleyl group.

The t-valent alicyclic hydrocarbon group is a group obtained by removing t hydrogen atoms from the structural formula of the alicyclic hydrocarbon. For example, as the monovalent aliphatic hydrocarbon group, a C _3-20 alicyclic hydrocarbon group is preferable, and examples thereof include 3 to 20 members such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group. (Preferably 3 to 15 members, particularly preferably 5 to 8 members) cycloalkyl group; 3 to 20 members (preferably 3 to 15 members, particularly preferably 5 to 8) such as cyclopentenyl group and cyclohexenyl group Member) degree cycloalkenyl group; perhydronaphthalen-1-yl group, norbornyl group, adamantyl group, tricyclo [5.2.1.0 ^2,6 ] decan-8-yl group, tetracyclo [4.4.0 .1, ^2,5 . And a bridged cyclic hydrocarbon group such as 1 ^7,10 ] dodecan-3-yl group.

The t-valent aromatic hydrocarbon group is a group obtained by removing t hydrogen atoms from the structural formula of the aromatic hydrocarbon. For example, the monovalent aromatic hydrocarbon group is preferably a C _6-14 (particularly C _6-10 ) aromatic hydrocarbon group, and examples thereof include a phenyl group and a naphthyl group.

  The compound represented by the formula (5) is preferably a polyoxyalkylene alkyl ether, for example, polyoxyethylene lauryl ether, polyoxyethylene tridecyl ether, polyoxyethylene myristyl ether, polyoxyethylene cetyl ether, polyoxyethylene isoester. Stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyldodecyl ether, polyoxyethylene alkyl or alkenyl ether such as polyoxyethylene behenyl ether; polyoxyethylene cholesteryl ether; polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether Such as polyoxyethylene alkylphenyl ether; polyoxypropylene butyl ether, polyoxypro Polyoxypropylene alkyl ethers such as lenmyristyl ether, polyoxypropylene cetyl ether, polyoxypropylene stearyl ether; polyoxyethylene polyoxypropylene butyl ether, polyoxyethylene polyoxypropylene lauryl ether, polyoxyethylene polyoxypropylene cetyl ether, poly Examples include polyoxyethylene polyoxypropylene alkyl ethers such as oxyethylene polyoxypropylene stearyl ether and polyoxyethylene polyoxypropylene decyl tetradecyl ether.

  Examples of the ether-ester type nonionic surfactant include polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, sorbitan monooleate, polyoxyethylene sorbite tetraoleate, polyoxyethylene monopalmitate Polyoxyethylene sorbitan fatty acid ester such as sorbitan, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate; polyoxyethylene glycerin fatty acid ester borate ester; polyoxyethylene (5) cetyl ether stearate, polyoxyethylene (10) Cetyl ether stearate and the like can be mentioned.

  Examples of the nitrogen-containing nonionic surfactant include polyoxyethylene alkylamines; fatty acid alkanolamides such as coconut oil fatty acid monoethanolamide, coconut oil fatty acid diethanolamide, and lauric acid diethanolamide.

As the surfactant, one having an HLB value (Hydorophile Lipophile Balance) of, for example, 8 to 18 (preferably 9 to 16, particularly preferably 10 to 15) is preferable from the viewpoint of excellent dispersibility. The HLB value is a value representing the balance between hydrophilicity and lipophilicity of the surfactant. In the present invention, the value calculated by the following equation based on the organic conceptual diagram method was used.
HLB value = inorganic value / organic value × 10

  The concentration of the surfactant in the reaction system is, for example, 0.001 to 1.0% by weight, preferably 0.01 to 0.5% by weight, particularly preferably 0.05 to 0.2% by weight. When the reaction in step 2 is performed in the presence of a surfactant having a concentration in the above range, the target compound can be selectively and efficiently produced, and the reaction products or the reaction product and the reaction substrate adhere and aggregate. Thus, the formation of a lump can be suppressed, and a uniform particulate carboxylic acid amide compound can be produced. On the other hand, when the concentration of the surfactant is below the above range, it is difficult to suppress the reaction product from adhering and aggregating to form a lump, and it is difficult to stir the reaction solution as the reaction proceeds. Thus, the composition of the reaction solution becomes non-uniform, so that the purity of the reaction product is lowered, and it is difficult to obtain a carboxylic acid amide having a good thickening and stabilizing effect.

  The reaction between the amic acid and the amine (2) is preferably performed in the presence of a solvent. Examples of the solvent include the same examples as the solvent used in Step 1. Therefore, the solvent used in Step 1 may be used in Step 2 as it is.

  The amount of the solvent used is, for example, about 3 to 10 times by weight, preferably 4 to 6 times by weight, based on the total amount of amic acid and amine (2). When the usage-amount of a solvent exceeds the said range, the density | concentration of a reaction component will become low and there exists a tendency for reaction rate to fall.

  The reaction of step 2 is usually performed under normal pressure. Further, the atmosphere of the reaction is not particularly limited as long as the reaction is not inhibited, and may be any of an air atmosphere, a nitrogen atmosphere, an argon atmosphere, and the like. The reaction temperature (or aging temperature) is, for example, about 30 to 70 ° C. The reaction time (or aging time) is, for example, about 0.5 to 20 hours. The reaction can be carried out by any method such as batch, semi-batch and continuous methods.

  After completion of the reaction, the obtained reaction product can be separated and purified by separation means such as filtration, concentration, distillation, extraction, crystallization, adsorption, recrystallization, column chromatography, etc., or a separation means combining these.

  In the production method of the present invention, the reaction between the amic acid and the amine is carried out in the presence of a surfactant, so even if the reaction proceeds, the reaction product is prevented from adhering and aggregating to form a lump. Since the reaction solution can be kept in a uniform state by stirring the reaction solution until the reaction is completed, the carboxylic acid amide compound has a narrow molecular weight distribution and high purity, and is excellent in thickening and stabilizing effect. Can be manufactured.

The carboxylic acid amide compound obtained by the production method of the present invention can self-associate by hydrogen bonding at the amide bond site to form a fiber-like self-assembly. Furthermore, since the R ¹ and R ² groups have an affinity for the fluid organic substance described later, the fluid organic substance is thickened, gelled, or stabilized by being compatible with the fluid organic substance. be able to. In particular, when the R ¹ and R ² groups in the carboxylic acid amide compound represented by the formula (4) are different from each other, since they have appropriate crystallinity, they have a thickening and stabilizing effect on a wider range of fluid organic substances. It can be demonstrated. That is, there is a wide range of selection of fluid organic substances that can provide a thickening and stabilizing effect. Then, the fluid organic substance can be thickened and stabilized stably over time. Therefore, the carboxylic acid amide compound is useful as a thickening stabilizer for fluid organic substances (more specifically, a thickening agent, a gelling agent, or a stabilizer) in, for example, cosmetics, paints, foods, and pharmaceuticals. It is.

  The flowable organic material is an organic material having a viscosity [25 ° C., viscosity (η) at a shear rate of 10 (1 / s)] of less than 0.1 Pa · s by a rheometer, for example, hydrocarbon oil (hexane, Cyclohexane, isododecane, benzene, toluene, polyalphaolefin, liquid paraffin, etc.), ethers (tetrahydrofuran, etc.), halogenated hydrocarbons (carbon tetrachloride, chlorobenzene, etc.), petroleum components (kerosene, gasoline, light oil, heavy oil, etc.), Animal and vegetable oils (sunflower oil, olive oil, soybean oil, corn oil, sunflower oil, beef tallow, jojoba oil, squalane, etc.), silicones (dimethylpolysiloxane, methylphenylpolysiloxane, etc.), esters (octyldodecyl oleate, octanoic acid) Cetyl, cetyl ethylhexanoate, glyceryl triisooctanoate, Neopentyl glycol diisooctanoate), aromatic carboxylic acid, pyridine and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited by these Examples.

Example 1 [Thickening Stabilizer (1) (Synthesis of 1,2,4,5-benzenetetracarboxylic acid bis (2-ethylhexylamide) bis (oleylamide)]
4. Dimroth condenser, nitrogen inlet, dropping funnel, thermometer, 100 mL 3-neck round bottom flask with 45 g of pyridine, 1,2,4,5-benzenetetracarboxylic acid-1,2: 4,5-dianhydride 0 g (0.023 mol) and 5.9 g (0.046 mol) of 2-ethylhexylamine were charged. The system temperature was set to 50 ° C. and aged for 1 hour. Thereafter, 5.8 g (0.046 mol) of diisopropylcarbodiimide was charged, followed by further aging for 1 hour.
Then, 0.07 g of polyoxyalkylene alkyl ether (HLB value: 12.7, trade name “Emulgen MS-110”, manufactured by Kao Corporation) as a surfactant (surfactant concentration in the reaction system: 0.1) % By weight) and 12.3 g (0.046 mol) of oleylamine was added dropwise with a dropping funnel. At the same time when oleylamine was dropped, a small gel-like reaction product (particle size of 1 to 2 mm) was successively deposited and dispersed in the reaction solution. The system temperature was set to 50 ° C. and aged for 2 hours. After aging, 45 g of 2-propanol was added dropwise. The crude liquid cooled to 20 ° C. is suction filtered, washed with methanol, and dried under reduced pressure at a temperature of 50 ° C. and a vacuum degree of 1.3 hPa for 8 hours using a vacuum dryer. , 4,5-bezenetetracarboxylic acid bis (2-ethylhexylamide) bis (oleylamide) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis (2-ethylhexylamide) -2, 19.6 g of a mixture of 5-bis (oleylamide) and 1,2,4,5-benzenetetracarboxylic acid-1,5-bis (2-ethylhexylamide) -2,4-bis (oleylamide)] (Yield: 87%). The structure of the reaction product was confirmed by ¹ H-NMR.
¹ H-NMR (400 MHz, CDCl ₃ ): δ 0.81-1.02 (m, 18H), 1.03-1.85 (m, 74H), 1.96-2.04 (m, 8H), 3.25-3.40 (m, 4H), 5.22- 5.51 (m, 4H), 8.5-9.5 (m, 2H)

  Further, the obtained 1,2,4,5-bezentetracarboxylic acid bis (2-ethylhexylamide) bis (oleylamide) is excellent in thickening and stabilizing effect (see WO2015 / 083740).

Comparative Example 1 [Thickening Stabilizer (1) (Synthesis of 1,2,4,5-benzenetetracarboxylic acid bis (2-ethylhexylamide) bis (dioleylamide)]
When the same procedure as in Example 1 was performed except that the surfactant was not added, a highly viscous reaction product (amorphous solid) was precipitated simultaneously with the dropwise addition of oleylamine, and agglomerated into several lumps. It was. Thereafter, in the same manner as in Example 1, the system temperature was set to 50 ° C., and aging was performed for 2 hours. After aging, 45 g of 2-propanol was added dropwise. The crude liquid cooled to 20 ° C. was suction filtered, washed with methanol, and dried under reduced pressure in a vacuum dryer at a temperature of 50 ° C. and a vacuum degree of 1.3 hPa for 8 hours to obtain a pale yellow powdery solid 1, 2, 4, 5-bezentetracarboxylic acid bis (2-ethylhexylamide) bis (oleylamide) [1,2,4,5-benzenetetracarboxylic acid-1,4-bis (2-ethylhexylamide) -2,5-bis (A mixture of (oleylamide) and 1,2,4,5-benzenetetracarboxylic acid-1,5-bis (2-ethylhexylamide) -2,4-bis (oleylamide)] was obtained. (Rate: 87%).

Claims (3)

The following formula (1) is added to benzenetetracarboxylic dianhydride.
R ¹ —NH ₂ (1)
(Wherein R ¹ represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (2):

(Wherein R ¹ is the same as above)
In the presence of a condensing agent and a surfactant, the following formula (3) is obtained.
R ² —NH ₂ (3)
(Wherein R ² represents an aliphatic hydrocarbon group having 6 or more carbon atoms)
Is reacted with an amine represented by the following formula (4):

(In the formula, R ¹ and R ² are the same as above. R ¹ and R ² may be the same or different.)
The manufacturing method of the carboxylic acid amide compound which obtains the carboxylic amide compound represented by these.   The method for producing a carboxylic acid amide compound according to claim 1, wherein the concentration of the surfactant in the reaction system is 0.001 to 1.0% by weight.   The method for producing a carboxylic acid amide compound according to claim 1 or 2, wherein the condensing agent is carbodiimide.